Intramolecular Sila-Matteson Rearrangement: a General Access to Silylated Heterocycles

Μέγεθος: px
Εμφάνιση ξεκινά από τη σελίδα:

Download "Intramolecular Sila-Matteson Rearrangement: a General Access to Silylated Heterocycles"

Transcript

1 Intramolecular Sila-Matteson Rearrangement: a General Access to Silylated Heterocycles Cyril François, Thomas Boddaert, Muriel Durandetti, Olivier Querolle, Luc Van Hijfte, Lieven Meerpoel, Patrick Angibaud, Jacques Maddaluno CNRS UMR 6014 COBRA & FR 3038 INC3M, Université de Rouen and INSA de Rouen, Mont St Aignan Cedex, France and Department of Medicinal Chemistry, Janssen, Campus de Maigremont, BP615, Val de Reuil, France Supporting Information 1. General Experimental Supplementary experiments: experimental conditions screening Supplementary methods: Details synthetic procedures for precursor preparations Supplementary methods: Details synthetic procedures for cyclisation steps Supplementary methods: Details synthetic procedures for the rearrangement study Supplementary figures: Plot of log (b/a) against Hammett constants ( ) Supplementary figures: 1 H and 13 C NMR spectra S1 -

2 1. General Experimental All reactions were conducted under an argon atmosphere unless otherwise stated and oven flamed glassware was used. THF was distilled under argon from sodium using benzophenone as indicator. Toluene was distilled over calcium hydride under a nitrogen atmosphere. Anhydrous acetonitrile and N,N-dimethylformamide were purchased from Fisher scientific and Carlo Erba respectively. All other solvents and commercially available reagents were used as received. Reactions were monitored by TLC performed using 0,25 mm E. Merck 5735 Kiegelsel silica gel coated aluminium plates (60F254) using UV radiation (254 nm) as visualizing agent and 7% ethanolic phosphomolybdic acid or aqueous KMnO 4 and heat as developing agent or by GC 24-m HP-methyl silicon capillary column. Flash column chromatography was carried out under pressure on Merck silica gel mesh. 1 H NMR and 13 C NMR spectra were recorded at 25 C on a Brucker Avance 300 or 200 MHz ( 1 H) and 75 or 50 MHz ( 13 C), and calibrated using solvent as internal standard ( H: CDCl ppm; C CDCl ppm). Splitting patterns are abbreviated as follows: singlet (s), doublet (d), triplet (t), quartet (q), multiplet (m), broad (br), apparent (ap) or a combination of these. IR spectra were recorded on a Perkin Elmer Spectrum 100 FT-IR spectrometer using a ZnSe plate (ATR). High resolution mass spectra (HRMS) were recorded on a Thermo Finnigan MAT95XP and accurate to ± Melting points were measured on a Kofler bench and are uncorrected. 2. Supplementary experiments: experimental conditions screening Halogen on the aromatic ring and leaving group on the side chain: entry X Z ratio (a/b) 1 I Cl 60:40 2 Br Cl 59:41 3 I I 60:40 4 I OMs 70:30 5 I OTs 75:25 - S2 -

3 Temperature and structure of the organometallic: entry RM temperature ratio (a/b) 1 n-buli (1.2 equiv.) -40 C 60:40 2 n-buli (1.2 equiv.) -78 C 60:40 3 n-buli (1.2 equiv.) -20 C 62:38 4 n-buli (1.2 equiv.) 0 C 60:40 5 t-buli (2.4 equiv.) -78 C 62:38 6 MeLi (1.2 equiv.) -40 C 54:46 7 MeLi.LiBr (1.2 equiv.) -40 C 55:45 8 i-prmgcl (1.8 equiv.) 0 C then 40 C 60:40 9 i-prmgcl.licl (1.8 equiv.) 0 C then 40 C 60:40 3. Supplementary methods: Details synthetic procedures for precursor preparations General procedure A: alkylation of phenol derivative To a solution of phenol (1.0 equiv.) in anhydrous acetonitrile (7 ml/mmol) were added K 2 CO 3 (3.0 equiv.) and. bis(chloromethyl)dimethylsilane (1.3 equiv.). Then the reaction mixture was heated under reflux until total disappearance of the starting material (TLC or GC). The medium was allowed to cool down to room temperature, filtered through a pad of celite and concentrated under reduced pressure. The crude mixture was finally purified by flash chromatography on silica gel using the appropriate mixture of eluents. General procedure B: alkylation of aniline derivatives To a solution of aniline (1.0 equiv.) in anhydrous DMF (5 ml/mmol) was added NaH (60% in oil, 1.3 equiv.). After 5 min. bis(chloromethyl)dimethylsilane (1.3 equiv.) was added pure, then the reaction mixture was heated at 80 C until total disappearance of the starting material (GC, 2-3h). The medium was allowed to cool down to room temperature and quenched with a saturated aqueous solution of NH 4 Cl and extracted with diethyl ether. The resulting organic phase was then washed three times with water, dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The crude mixture was finally purified by flash chromatography on silica gel using the appropriate mixture of eluents. - S3 -

4 tert-butyl ((chloromethyl)dimethylsilyl)methyl(2-iodophenyl)carbamate 6 From the protected iodoaniline 1 (638 mg, 2.00 mmol), following the general procedure B, the halogenoaryl 6 was obtained as a colorless oil (632 mg, 72%). Rf (5% diethyl ether/pentane): 0.52; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.84 (d, J = 7.4 Hz, 1H), 7.33 (dd, J = 7.5, 7.4 Hz, 1H), 7.19 (d, J = 7.6 Hz, 1H), 6.96 (dd, J = 7.6, 7.5 Hz, 1H), (m, 2H), (m, 2H), 1.53 (s, 1.5H), 1.33 (s, 7.5H), 0.26 (s, 3H), 0.24 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ = 154.7, 146.8, 139.6, 129.2, 128.8, 128.6, 99.4, 80.3, 39.7, 31.5, 28.3 (3C), -3.4, -3.6; IR (neat) : υ 2974, 2931, 1690, 1365, 839, 758 cm -1 ; HRMS (ESI+): theor (calc. for C 15 H 24 NO 2 SiClI), meas (chloromethyl)((2-iodophenoxy)methyl)dimethylsilane 7 From 2-iodophenol (1.54 g, 7.00 mmol), following the general procedure A, the halogenoaryl 7 was obtained as a colorless oil (1.95 g, 82%). Rf (pentane): 0.68; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.74 (dd, J = 7.7, 1.6 Hz, 1H), 7.31 (ddd, J = 8.3, 7.5, 1.6 Hz, 1H), 6.91 (dd, J = 8.3, 1.2 Hz, 1H), 6.70 (ddd, J = 7.7, 7.5, 1.2 Hz, 1H), 3.75 (s, 2H), 3.04 (s, 2H), 0.34 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 159.3, 139.3, 129.6, 122.5, 111.3, 88.6, 59.5, 28.8, -5.7 (2C); IR (neat) : υ 2960, 2897, 1468, 1233, 1017, 839, 745, 643 cm -1 ; Elem. anal.: %C theor meas , %H theor meas tert-butyl 2-bromo-5-(trifluoromethyl)phenyl(((chloromethyl)dimethylsilyl)methyl)carbamate 12 1 Boger, D. L.; McKie, J. A. J. Org. Chem. 1995, 60, S4 -

5 From the protected bromoaniline 2 (3.20 g, 9.40 mmol), following the general procedure B, the halogenoaryl 12 was obtained as a colorless oil (2.73 g, 63%). Rf (5% diethyl ether/pentane): 0.62; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.72 (d, J = 8.4 Hz, 1H), 7.46 (s, 1H), 7.37 (d, J = 8.4 Hz, 1H), 3.17 (A of AB quartet, J = 15.3 Hz, 1H), 2.94 (B of AB quartet, J = 15.3 Hz, 1H), (m, 2H), 1.55 (s, 1H), 1.33 (s, 8H), 0.24 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 154.4, 144.2, 134.1, (q, J = 30Hz), 127.3, (q, J = 3Hz), (q, J = 3Hz), (q, J = 270Hz), 81.0, 39.7, 31.2, 28.1 (3C), -3.7, -3.8; IR (neat) : υ 2978, 1699, 1334, 1129, 823 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 23 NO 2 SiBrClF 3 ), meas tert-butyl 2-bromo-5-chlorophenyl(((chloromethyl)dimethylsilyl)methyl)carbamate 13 From the protected bromoaniline 3 (900 mg, 2.93 mmol), following the general procedure B, the halogenoaryl 13 was obtained as a colorless oil (912 mg, 73%). Rf (5% diethyl ether/pentane): 0.61; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.50 (d, J = 8.4 Hz, 1H), 7.21 (d, J = 2.4 Hz, 1H), 7.10 (dd, J = 8.4, 2.4 Hz, 1H), 3.12 (A of AB quartet, J = 15.4 Hz, 1H), 2.94 (B of AB quartet, J = 15.4 Hz, 1H), (m, 2H), 1.34 (s, 9H), 0.25 (s, 3H), 0.24 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ = 154.4, 144.5, 134.0, 133.5, 129.5, 128.5, 121.3, 80.7, 39.8, 31.2, 28.1 (3C), -3.7, -3.8; IR (neat) : υ 2980, 2932, 2097, 1695, 1364, 1144, 838, 459 cm -1 ; HRMS (ESI+): theor (calc. for C 15 H 23 NO 2 SiCl 2 Br), meas tert-butyl 2-bromo-5-fluorophenyl(((chloromethyl)dimethylsilyl)methyl)carbamate 14 From the protected bromoaniline 2 (2.05 g, 7.06 mmol), following the general procedure B, the halogenoaryl 14 was obtained as a colorless oil (1.96 g, 67%). Rf (5% diethyl ether/pentane): 0.67; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.53 (dd, J = 8.7, 5.9 Hz, 1H), 6.97 (dd, J = 9.0, 2.7 Hz, 1H), 6.89 (ddd, J = 8.7, 8.3, 2.7 Hz, 1H), 3.15 (A of AB quartet, J = 15.2 Hz, 1H), 2.93 (B of AB quartet, J = 15.2 Hz, 1H), 2.88 (A of AB quartet, J = 13.8 Hz, 1H), 2.82 (B of AB 2 Thansandote, P.; Hulcoop, D. H.; Langer, M.; Lautens, M. J. Org. Chem. 2009, 74, Darnbrough, S.; Mervic, M.; Condon, S.; Burns, C. Synthetic Comm. 2001, 31, S5 -

6 quartet, J = 13.8 Hz, 1H), 1.53 (br s, 1H), 1.34 (s, 8H), 0.24 (s, 3H), 0.23 (s, 3H) ; 13 C NMR (75 MHz, CDCl 3 ) δ = (d, J = 247 Hz), 154.4, (d, J = 10 Hz), (d, J = 8 Hz), (d, J = 4 Hz), (d, J = 22 Hz), (d, J = 22 Hz), 80.6, 39.6, 31.1, 28.1 (3C), -3.8, -3.9; IR (neat) : υ 2980, 1697, 1472, 1250, 1161, 840, 599, 468 cm -1 ; HRMS (ESI+): theor (calc. for C 15 H 23 NO 2 SiClBrF), meas tert-butyl 2-bromo-4-(trifluoromethyl)phenyl(((chloromethyl)dimethylsilyl)methyl)carbamate 15 From the protected bromoaniline 4 (1.60 g, 4.70 mmol), following the general procedure B, the halogenoaryl 15 was obtained as a colorless oil (990 mg, 46%). Rf (5% diethyl ether/pentane): 0.55; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.86 (s, 1H), 7.56 (d, J = 8.1 Hz, 1H), 7.34 (d, J = 8.1 Hz, 1H), 3.15 (A of AB quartet, J = 15 Hz, 1H), 2.92 (B of AB quartet, J = 15 Hz, 1H), 2.89 (A of AB quartet, J = 13.6 Hz, 1H), 2.86 (B of AB quartet, J = 13.6 Hz, 1H), 1.54 (s, 1.5H), 1.34 (s, 7.5H), 0.25 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 154.3, 146.8, (q, J = 4 Hz), (q, J = 34 Hz), 129.8, (q, J = 3 Hz), 123.6, (q, J = 271 Hz), 81.0, 39.7, 31.2, 28.1 (3C), -3.7, -3.8; IR (neat) : υ 2975, 2928, 1699, 1321, 1128, 837 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 23 NO 2 F 3 SiBrCl), meas tert-butyl 2-bromo-4-fluorophenyl(((chloromethyl)dimethylsilyl)methyl)carbamate 16 From the protected bromoaniline 2 (867 mg, 2.99 mmol), following the general procedure B, the halogenoaryl 16 was obtained as a colorless oil (868 mg, 71%). Rf (5% diethyl ether/pentane): 0.51; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.32 (dd, J = 7.9, 2.7 Hz, 1H), 7.19 (dd, J = 8.7, 5.6 Hz, 1H), 7.01 (ddd, J = 8.7, 7.9, 2.7 Hz, 1H), 3.17 (A of AB quartet, J = 15.1 Hz, 1H), 2.88 (B of AB quartet, J = 15.1 Hz, 1H), 2.86 (A of AB quartet, J = 13.6 Hz, 1H), 2.81 (B of AB quartet, J = 13.6 Hz, 1H), 1.32 (s, 9H), 0.23 (s, 3H), 0.22 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ = (d, J = 249 Hz), 154.9, 139.9, (d, J = 9 Hz), (d, J = 10 Hz), (d, J = 25 Hz), 4 Bellezza, F.; Cipiciani, A.; Ruzziconi, R.; Spizzichino, S. J. Fluorine Chem. 2008, 129, S6 -

7 115.3 (d, J = 22 Hz), 80.5, 39.7, 31.2, 28.2 (3C), -3.7, -3.8; IR (neat) : υ 2977, 1697, 1489, 1367, 845 cm -1 ; HRMS (ESI+): theor (calc. for C 15 H 23 NO 2 SiClBrF), meas tert-butyl 2-bromo-4-methoxyphenyl(((chloromethyl)dimethylsilyl)methyl)carbamate 17 From the protected bromoaniline 2 (819 mg, 2.71 mmol), following the general procedure B, the halogenoaryl 17 was obtained as a colorless oil (815 mg, 71%). Rf (5% diethyl ether/pentane): 0.35; 1 H NMR (300 MHz, CDCl 3 ) δ = (m, 2H), 6.80 (dd, J = 8.7, 2.7 Hz, 1H), 3.79 (s, 3H), 3.19 (A of AB quartet, J = 15.3 Hz, 1H), 2.89 (B of AB quartet, J = 15.3 Hz, 1H), 2.82 (A of AB quartet, J = 13.7 Hz, 1H), 2.79 (A of AB quartet, J = 13.7 Hz, 1H), 1.32 (s, 9H), 0.22 (s, 3H), 0.20 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ = 158.7, 155.2, 136.4, 129.7, 123.5, 118.1, 113.9, 80.1, 55.8, 39.8, 31.3, 28.2 (3C), -3.8, -3.9; IR (neat) : υ 2975, 1689, 1493, 1365, 1165, 840, 601, 459 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 26 NO 3 SiBrCl), meas tert-butyl 2-bromo-5-methoxyphenyl(((chloromethyl)dimethylsilyl)methyl)carbamate 18 From the protected bromoaniline 5 (903 mg, 2.99 mmol), following the general procedure B, the halogenoaryl 18 was obtained as a colorless oil (912 mg, 72%). Rf (5% diethyl ether/pentane): 0.36; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.44 (d, J = 8.7 Hz, 1H), 6.77 (d, J = 3.0 Hz, 1H), 6.69 (dd, J = 8.7, 3.0 Hz, 1H), 3.79 (s, 3H), 3.17 (A of AB quartet, J = 15 Hz, 1H), 2.96 (B of AB quartet, J = 15 Hz, 1H), 2.87 (A of AB quartet, J = 13.6 Hz, 1H), 2.81 (B of AB quartet, J = 13.6 Hz, 1H), 1.53 (br s, 1.5H), 1.34 (s, 7.5H), 0.23 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 159.4, 154.8, 144.1, 133.4, 115.4, 114.1, 113.6, 80.3, 55.7, 39.7, 31.3, 28.2 (3C), -3.7, -3.9; IR (neat) : υ 2971, 1692, 1364, 1165, 839, 614 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 26 NO 3 SiBrCl), meas Wu, T. Y.-H.; Li, Y.; Cortez, A.; Zou, Y.; Mishra, P.; Zhang, X.; Skibinski, D.; Singh, M.; Valiante, N. Novartis AG. PCT Int. Appl. WO/2009/ S7 -

8 Compound 39 To a solution of 2-bromo-5-nitroaniline (1.14 g, 5.24 mmol, 1.0 equiv.) in anhydrous dichloromethane (50 ml) were added Boc 2 O (2.86 g, 13.1 mmol, 2.5 equiv.) and a catalytic amount of N,N-dimethyl-4- aminopyridine. After total disappearance of the starting material (TLC), the reaction mixture was concentrated under reduced pressure. The crude mixture was purified by flash chromatography on silica gel (10% diethyl ether/pentane) to give compound 39, as a yellow solid (2.05 g, 94%). Rf (10% diethyl ether/pentane): 0.38; 1 H NMR (300 MHz, CDCl 3 ) δ = (m, 2H), 7.80 (d, J = 8.6 Hz, 1H), 1.39 (s, 18H); 13 C NMR (75 MHz, CDCl 3 ) δ = (2C), 147.2, 139.8, 133.4, 131.2, 124.9, 123.6, 83.9 (2C), 27.7 (6C); IR (neat) : υ 2980, 2939, 1699, 1525, 1342, 1115, 740 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 21 N 2 O 6 BrK), meas ; mp: 100 C. Compound 40 To a solution of protected aniline 39 (2.09 g, 5.0 mmol, 1.0 equiv.) in anhydrous acetone (100 ml) were added Zn powder (3.93 g, 60 mmol, 12.0 equiv.) and ammonium chloride (5.35 g, 100 mmol, 20 equiv.). The reaction mixture was then heated under reflux for 6h. The medium was allowed to cool down to room temperature and quenched with water and extracted with dichloromethane. The resulting organic phase was dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure to give the crude mixture which was directly engaged in the next step. To a solution of the resulting bis-aniline (1.0 equiv.) in anhydrous DMF (40 ml) were added methyliodide (3.55 g, 25.0 mmol, 5.0 equiv.) and K 2 CO 3 (1.69 g, 12.3 mmol, 2.5 equiv.). After 20h at room temperature, the reaction mixture was quenched with a saturated aqueous solution of NH 4 Cl and extracted with diethyl ether. The resulting organic phase was washed five times with water, dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The crude mixture was purified by flash chromatography on silica gel (30% diethyl ether/pentane) to give dimethylaniline 40 as a yellow oil (747 mg, 36% over 2 steps). Rf (30% diethyl ether/pentane): 0.30; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.34 (d, J = 8.9 Hz, 1H), (m, 2H), 2.90 (s, 6H), 1.41 (s, 18H); 13 C NMR (75 MHz, CDCl 3 ) δ = (2C), 150.3, 138.7, 132.3, 113.6, 113.1, 109.0, 82.4 (2C), 40.4 (2C), (6C); IR (neat) : υ 2975, 1753, 1366, 1114, 805 cm -1 ; HRMS (ESI+): theor (calc. for C 18 H 28 N 2 O 4 Br), meas S8 -

9 tert-butyl 2-bromo-5-(dimethylamino)phenylcarbamate 41 To a solution of protected bis-aniline 40 (564 mg, 1.4 mmol, 1.0 equiv.) in anhydrous methanol (10 ml) was added K 2 CO 3 (563 mg, 4.1 mmol, 3.0 equiv.). The reaction mixture was then heated under reflux for 3h. The medium was allowed to cool down to room temperature and quenched with water and extracted with ethyl acetate. The resulting organic phase was dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The crude mixture was purified by flash chromatography on silica gel (10% diethyl ether/pentane) to give the carbamate 41 as a yellow oil (403 mg, 94%). Rf (30% diethyl ether/pentane): 0.81; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.64 (d, J = 2.9 Hz, 1H), 7.26 (d, J = 8.9 Hz, 1H), 6.97 (br s, 1H), 6.26 (dd, J = 8.9, 2.9 Hz, 1H), 2.94 (s, 6H), 1.55 (s, 9H) ; 13 C NMR (75 MHz, CDCl 3 ) δ = 152.2, 150.4, 136.3, 131.8, 108.2, 103.6, 98.4, 80.5, 40.4 (2C), 28.2 (3C); IR (neat) : υ 3414, 2977, 2793, 1729, 1518, 1148, 765 cm -1 ; HRMS (ESI+): theor (calc. for C 13 H 20 N 2 O 2 Br), meas tert-butyl 2-bromo-5-(dimethyllamino)phenyl(((chloromethyl)dimethylsilyl)methyl)carbamate 19 N Br N Si Cl Boc 19 C 17 H 28 BrClN 2 O 2 Si MW = g/mol From the protected bromoaniline 41 (354 mg, 1.12 mmol), following the general procedure B, the halogenoaryl 19 was obtained as a white solid (300 mg, 62%). Rf (10% diethyl ether/pentane): 0.57; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.33 (d, J = 8.9 Hz, 1H), 6.53 (d, J = 2.9 Hz, 1H), 7.47 (dd, J = 8.9, 2.9 Hz, 1H), 3.18 (A of AB quartet, J = 15.3 Hz, 1H), 2.97 (B of AB quartet, J = 15.3 Hz, 1H), 2.93 (s, 6H), 2.87 (A of AB quartet, J = 13.6 Hz, 1H), 2.80 (B of AB quartet, J = 13.6 Hz, 1H), 1.53 (s, 1.5H), 1.35 (s, 7.5H), 0.23 (s, 3H), 0.23 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ = 155.0, 150.4, 143.5, 132.9, 113.0, 112.4, 108.5, 79.9, 40.4 (2C), 39.6, 31.3, 28.1 (3C), -3.8, -4.0; IR (neat) : υ 2980, 2927, 2805, 1688, 1364, 1145, 787 cm -1 ; HRMS (ESI+): theor (calc. for C 17 H 29 N 2 O 2 SiClBr), meas ; mp: 64 C. - S9 -

10 tert-butyl 2-bromo-4-methylphenyl(((chloromethyl)dimethylsilyl)methyl)carbamate 20 From the protected bromoaniline 2 (757 mg, 2.65 mmol), following the general procedure B, the halogenoaryl 20 was obtained as a colorless oil (756 mg, 70%) Rf (5% diethyl ether/pentane): 0.68; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.37 (br s, 1H), 7.06 (br s, 2H), 3.17 (A of AB quartet, J = 15.3 Hz, 1H), 2.90 (B of AB quartet, J = 15.3 Hz, 1H), 2.84 (A of AB quartet, J = 13.5 Hz, 1H), 2.88 (B of AB quartet, J = 13.5 Hz, 1H), 2.30 (s, 3H), 1.32 (s, 9H), 0.21 (s, 3H), 0.20 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ = 154.8, 140.5, 138.3, 133.4, , , 122.4, 79.8, 39.5, 31.0, 28.0 (3C), 20.6, -4.0, -4.1; IR (neat) : υ 2980, 2928, 1690, 1364, 819, 452 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 26 NO 2 SiClBr), meas tert-butyl 2-bromo-5-methylphenyl(((chloromethyl)dimethylsilyl)methyl)carbamate 21 From the protected bromoaniline 5 (429 mg, 1.50 mmol), following the general procedure B, the halogenoaryl 21 was obtained as a colorless oil (416 mg, 68%) Rf (5% diethyl ether/pentane): 0.55; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.40 (d, J = 8.4 Hz, 1H), 7.00 (s, 1H), 6.88 (d, J = 8.4 Hz, 1H), 3.12 (A of AB quartet, J =15.2 Hz, 1H), 2.93 (B of AB quartet, J = 15.2 Hz, 1H), 2.83 (A of AB quartet, J = 13.6 Hz, 1H), 2.77 (B of AB quartet, J = 13.6 Hz, 1H), 2.27 (s, 3H), 1.31 (s, 9H), 0.22 (s, 3H), 0.20 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ =154.6, 142.8, 138.0, 132.6, 129.6, 129.0, 119.3, 79.9, 39.5, 31.1, 27.9 (3C), 20.7, -4.0, -4.1; IR (neat) : υ 2980, 2934, 1692, 1364, 1155, 840, 460 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 26 NO 2 SiClBr), meas Allyl ((chloromethyl)dimethylsilyl)methyl(2-iodophenyl)carbamate 32 - S10 -

11 From the protected bromoaniline 6 (872 mg, 2.88 mmol), following the general procedure B, the halogenoaryl 32 was obtained as a colorless oil (758 mg, 62%). Rf (5% diethyl ether/pentane): 0.44; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.87 (dd, J = 7.8, 1.5 Hz, 1H), 7.37 (ddd, J = 7.8, 7.5, 1.5 Hz, 1H), (m, 1H), 7.01 (ddd, J = 7.8, 7.5, 1.8 Hz, 1H), (m, 1H), (m, 2H), 4.53 (dd, J = 3.6, 1.5 Hz, 2H), 3.32 (A of AB quartet, J = 15.2 Hz, 1H), 2.88 (B of AB quartet, J = 15.2 Hz, 1H), (m, 2H), 0.28 (s, 3H), 0.26 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ = 155.2, 145.9, 139.7, 132.6, 129.3, 129.0, 128.7, 116.9, 99.0, 66.7, 40.4, 31.1, -3.6, - 3.7; IR (neat) : υ 2954, 1699, 1469, 839, 761 cm -1 ; HRMS (ESI+): theor (calc. for C 14 H 20 NO 2 SiClI), meas N-(((chloromethyl)dimethylsilyl)methyl)-N-(2-iodophenyl)-4-methylbenzenesulfonamide 33 From the protected iodoaniline 7 (1.11 g, 2.97 mmol), following the general procedure B, the halogenoaryl 33 was obtained as a white solid (852 mg, 58%). Rf (5% diethyl ether/pentane): 0.13; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.95 (dd, J = 7.8, 1.2 Hz, 1H), 7.59 (d, J = 8.1 Hz, 2H), 7.30 (d, J = 8.1 Hz, 2H), (m, 1H), 7.03 (ddd, J = 7.8, 7.5, 1.5 Hz, 1H), 6.75 (dd, J = 7.8, 1.5 Hz, 1H), 3.46 (A of AB quartet, J = 14.8 Hz, 1H), 2.82 (B of AB quartet, J = 14.8 Hz, 1H), 2.64 (A of AB quartet, J = 13.8 Hz, 1H), 2.54 (B of AB quartet, J = 13.8 Hz, 1H), 2.46 (s, 3H), 0.06 (s, 3H), 0.04 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ = 144.1, 143.6, 140.7, 133.2, 130.0, (2C), (2C), 128.8, 128.6, 103.1, 40.0, 29.5, 21.7, -4.5 (2C); IR (neat) : υ 3059, 2943, 1345, 1160, 816, 711, 650 cm -1 ; HRMS (ESI+): theor (calc. for C 17 H 22 NO 2 SiSClI), meas ; mp: 98 C. N-(((chloromethyl)dimethylsilyl)methyl)-N-(2-iodophenyl)methanesulfonamide 34 6 Lebel, H.; Leogane, O. Org. Lett. 2006, 8, Zenner, J. M.; Larock, R. C. J. Org. Chem. 1999, 64, S11 -

12 From the protected iodoaniline 8 (888 mg, 2.99 mmol), following the general procedure B, the halogenoaryl 34 was obtained as a colorless oil (672 mg, 54%). Rf (50% diethyl ether/pentane): 0.47; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.93 (d, J = 7.9 Hz, 1H), (m, 2H), (m, 1H), 3.47 (A of AB quartet, J = 20 Hz, 1H), 3.27 (B of AB quartet, J = 20 Hz, 1H), 3.08 (s, 3H), 2.72 (A of AB quartet, J = 14 Hz, 1H), 2.60 (B of AB quartet, J = 14 Hz, 1H), 0.09 (s, 3H), 0.06 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ = 143.1, 140.6, 130.1, 129.7, 129.3, 101.7, 39.4, 37.5, 29.3, -4.7, -4.8; IR (neat) : υ 2930, 1332, 1148, 782, 672 cm -1 ; HRMS (ESI+): theor (calc. for C 11 H 18 NO 2 SiSClI), meas Supplementary methods: Details synthetic procedures for cyclisation steps General procedure C: cyclisation using n-butyllithium (Conditions A) To a solution of halogenoaryl (1.0 equiv.) in anhydrous THF (10 ml/mmol) was added dropwise at -40 C a solution of n-buli in hexane (1.6 M, 1.2 equiv.). After 1h, the reaction mixture was quenched at -40 C with a saturated aqueous solution of NH 4 Cl, allowed to warm up to room temperature and extracted with diethyl ether. The resulting organic phase was then dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The crude mixture was finally purified by flash chromatography on silica gel using the appropriate mixture of eluents. General procedure D: cyclisation using t-butyllithium (Conditions B) To a solution of halogenoaryl (1.0 equiv.) in anhydrous THF (10 ml/mmol) was added dropwise at -78 C a solution of t-buli in hexane (1.7 M, 2.4 equiv.). After 1h, the reaction mixture was quenched at -78 C with a saturated aqueous solution of NH 4 Cl, allowed to warm up to room temperature and extracted with diethyl ether. The resulting organic phase was then dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The crude mixture was finally purified by flash chromatography on silica gel using the appropriate mixture of eluents. tert-butyl 3,3-dimethyl-3,4-dihydrobenzo[e][1,3]azasiline-1(2H)-carboxylate 4a tert-butyl 4,4-dimethyl-3,4-dihydrobenzo[b][1,4]azasiline-1(2H)-carboxylate 4b 8 Sakamoto, T.; Kondo, Y.; Iwashita, S.; Nagano, T.; Yamanaka, H. Chem. Pharm. Bull. 1988, 36, S12 -

13 From the halogenoaryl 6 (559 mg, 1.27 mmol), following the general procedure C, the silylated compound 4a was obtained as a white solid (141 mg, 40%). Rf (5% diethyl ether/pentane): 0.29; 1 H NMR (300 MHz, CDCl 3 ) δ = (m, 4H), 3.05 (s, 2H), 1.94 (s, 2H) 1.47 (s, 9H), 0.10 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 155.1, 140.9, 134.1, 130.0, 127.3, 125.8, 125.3, 79.9, 35.4, 28.4 (3C), 19.2, -2.7 (2C); IR (neat) : υ 2970, 1681, 1363, 1155, 822, 751 cm -1 ; HRMS (ESI+): theor (calc. for C 15 H 24 NO 2 Si), meas ; mp: 102 C. From the halogenoaryl 6 (559 mg, 1.27 mmol), following the general procedure C, the silylated compound 4b was obtained as a colorless oil (155 mg, 44%). Rf (5% diethyl ether/pentane): 0.39; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.41 (d, J = 7.1 Hz, 1H), (m, 2H), (m, 1H), (m, 2H), 1.47 (s, 9H), (m, 2H), 0.26 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 154.1, 148.6, 133.5, 130.6, 128.9, 126.0, 124.7, 80.1, 45.0, 28.4 (3C), 13.8, -1.2 (2C); IR (neat) : υ 2980, 1694, 1365, 1149, 832 cm -1 ; HRMS (ESI+): theor (calc. for C 15 H 24 NO 2 Si), meas ,3-dimethyl-3,4-dihydro-2H-benzo[e][1,3]oxasiline 5a 4,4-dimethyl-3,4-dihydro-2H-benzo[b][1,4]oxasiline 5b From the halogenoaryl 7 (680 mg, 2.00 mmol), following the general procedure C, the silylated compound 5a was obtained as a colorless oil (183 mg, 51%). Rf (pentane): 0.23; 1 H NMR (300 MHz, CDCl 3 ) δ = (m, 2H), (m, 2H), 3.76 (s, 2H), 2.00 (s, 2H), 0.17 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 158.2, 131.9, 128.1, 126.6, 122.7, 119.6, 63.7, 16.3, -3.1 (2C); IR (neat) : υ 2952, 2872, 1477, 1245, 1210, 973, 822, 742 cm -1 ; HRMS (ESI+): theor (calc. for C 10 H 15 OSi), meas From the halogenoaryl 7 (680 mg, 2.00 mmol), following the general procedure C, the silylated compound 5b was obtained as a colorless oil (122 mg, 34%). - S13 -

14 Rf (pentane): 0.37; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.36 (dd, J = 7.2, 1.7 Hz, 1H), (m, 1H), 6.95 (td ap, J = 7.2, 1.2 Hz, 1H), 6.83 (d, J = 8.2 Hz, 1H), (m, 2H), (m, 2H), 0.30 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 164.6, 134.7, 130.9, 121.6, 121.1, 117.6, 66.7, 13.8, -1.4 (2C); IR (neat) : υ 2952, 2862, 1432, 1266, 1215, 1039, 757 cm -1 ; HRMS (ESI+): theor (calc. for C 10 H 15 OSi), meas tert-butyl-3,3-dimethyl-7-(trifluoromethyl)-3,4-dihydrobenzo[e][1,3]azasiline-1(2h)-carboxylate 22a tert-butyl 4,4-dimethyl-7-(trifluoromethyl)-3,4-dihydrobenzo[b][1,4]azasiline-1(2H)-carboxylate 22b From the halogenoaryl 12 (359 mg, 0.78 mmol), following the general procedure C, the silylated compound 22a was obtained as a white solid (120 mg, 45%). From the halogenoaryl 12 (554 mg, 1.20 mmol), following the general procedure D, the silylated compound 22a was obtained as a white solid (269 mg, 65%). Rf (5% diethyl ether/pentane): 0.34; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.44 (br s, 1H), 7.30 (d, J = 7.8 Hz, 1H), 7.19 (d, J = 7.8 Hz, 1H), 3.06 (s, 2H), 2.00 (s, 2H), 1.44 (s, 9H), 0.12 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 154.8, 141.0, 138.6, 130.3, (q, J = 32 Hz), (q, J = 4 Hz), (q, J = 270 Hz), (q, J = 4 Hz), 80.6, 34.8, 28.3 (3C), 19.7, -2.8 (2C); IR (neat) : υ 2976, 1693, 1329, 1120, 837, 688 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 23 NO 2 F 3 Si), meas ; mp: 67 C. From the halogenoaryl 12 (359 mg, 0.78 mmol), following the general procedure C, the silylated compound 22b was obtained as a colorless oil (19 mg, 7%). From the halogenoaryl 12 (554 mg, 1.20 mmol), following the general procedure D, the silylated compound 22b was obtained as a colorless oil (27 mg, 7%). Rf (5% diethyl ether/pentane): 0.47; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.61 (br s, 1H), 7.50 (d, J = 7.8 Hz, 1H), 7.36 (d, J = 7.8 Hz, 1H), (m, 2H), 1.47 (s, 9H), (m, 2H), 0.28 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 153.8, 149.0, 135.2, 134.2, (q, J = 32 Hz), (q, J = 272 Hz), (q, J = 4 Hz), (q, J = 4 Hz), 81.1, 44.9, 28.4 (3C), 13.7, -1.3 (2C); IR (neat) : υ 2936, - S14 -

15 2850, 1692, 1329, 1167, 1129, 838 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 23 NO 2 F 3 Si), meas tert-butyl 7-chloro-3,3-dimethyl-3,4-dihydrobenzo[e][1,3]azasiline-1(2H)-carboxylate 23a tert-butyl 7-chloro-4,4-dimethyl-3,4-dihydrobenzo[b][1,4]azasiline-1(2H)-carboxylate 23b From the halogenoaryl 13 (609 mg, 1.42 mmol), following the general procedure C, the silylated compound 23a was obtained as a white solid (279 mg, 63%). From the halogenoaryl 13 (895 mg, 2.09 mmol), following the general procedure D, the silylated compound 23a was obtained as a white solid (458 mg, 70%). Rf (5% diethyl ether/pentane): 0.35; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.19 (br s, 1H), (m, 2H), 3.02 (s, 2H), 1.90 (s, 2H), 1.45 (s, 9H), 0.10 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 154.7, 141.7, 132.7, 130.8, 130.2, 127.5, 125.8, 80.4, 35.0, 28.4 (3C), 18.8, -2.7 (2C); IR (neat) : υ 2976, 2949, 1688, 1344, 1158, 835, 616 cm -1 ; HRMS (ESI+): theor (calc. for C 15 H 23 NO 2 SiCl), meas , mp : 88 C. From the halogenoaryl 13 (609 mg, 1.42 mmol), following the general procedure C, the silylated compound 23b was obtained as a colorless oil (50 mg, 11%). From the halogenoaryl 13 (895 mg, 2.09 mmol), following the general procedure D, the silylated compound 23b was obtained as a colorless oil (75 mg, 11%). Rf (5% diethyl ether/pentane): 0.49; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.37 (d, J = 1.9 Hz, 1H), 7.31 (d, J = 7.9 Hz, 1H), 7.11 (dd, J = 7.9, 1.9 Hz, 1H), (m, 2H), 1.48 (s, 9H), (m, 2H), 0.25 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 153.8, 149.7, 134.7, 134.6, 128.9, 126.2, 125.0, 80.8, 45.0, 28.4 (3C), 13.7, -1.2 (2C); IR (neat) : υ 2976, 2899, 1696, 1365, 1149, 828 cm -1 ; HRMS (ESI+): theor (calc. for C 15 H 23 NO 2 SiCl), meas S15 -

16 tert-butyl 7-fluoro-3,3-dimethyl-3,4-dihydrobenzo[e][1,3]azasiline-1(2H)-carboxylate 24a tert-butyl 7-fluoro-4,4-dimethyl-3,4-dihydrobenzo[b][1,4]azasiline-1(2H)-carboxylate 24b From the halogenoaryl 14 (1.23 g, 2.99 mmol), following the general procedure C, the silylated compound 24a was obtained as a white solid (371 mg, 42%). Rf (5% diethyl ether/pentane): 0.34; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.02 (dd, J = 8.4, 6.3 Hz, 1H), (m, 1H), 6.79 (dt ap, J = 8.4, 2.7 Hz, 1H), 3.03 (s, 2H), 1.89 (s, 2H), 1.45 (s, 9H), 0.10 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = (d, J = 241 Hz), 154.8, (d, J = 10 Hz), (d, J = 8 Hz), (d, J = 3 Hz), (d, J = 22 Hz), (d, J = 21 Hz), 80.3, 35.1, 28.4 (3C), 18.4, -2.8 (2C); IR (neat) : υ 2975, 1692, 1365, 1155, 833, 460 cm -1 ; HRMS (ESI+): theor (calc. for C 15 H 23 NO 2 FSi), meas ; mp: 65 C. F Si N Boc 24b C 15 H 22 FNO 2 Si MW = g/mol From the halogenoaryl 14 (1.23 g, 2.99 mmol), following the general procedure C, the silylated compound 24b was obtained as a colorless oil (280 mg, 32%). Rf (5% diethyl ether/pentane): 0.47; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.33 (dd, J = 8.4, 1.2 Hz, 1H), (m, 1H), 6.86 (ddd, 8.4, 8.2, 2.3 Hz, 1H), (m, 2H), 1.48 (s, 9H), (m, 2H), 0.24 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = (d, J = 244 Hz), 153.7, (d, J = 10 Hz), (d, J = 8 Hz), (d, J = 4 Hz), (d, J = 22 Hz), (d, J = 22 Hz), 80.7, 45.0, 28.3 (3C), 13.6, -1.1 (2C); IR (neat) : υ 2970, 1697, 1366, 1143, 833, 467 cm -1 ; HRMS (ESI+): theor (calc. for C 15 H 23 NO 2 FSi), meas tert-butyl-3,3-dimethyl-6-(trifluoromethyl)-3,4-dihydrobenzo[e][1,3]azasiline-1(2h)-carboxylate 25a tert-butyl-4,4-dimethyl-6-(trifluoromethyl)-3,4-dihydrobenzo[b][1,4]azasiline-1(2h)-carboxylate 25b From the halogenoaryl 15 (860 mg, 1.87 mmol), following the general procedure D, the silylated compound 25a was obtained as a white solid (438 mg, 68%). - S16 -

17 Rf (5% diethyl ether/pentane): 0.39; 1 H NMR (300 MHz, CDCl 3 ) δ = (m, 3H), 3.05 (s, 2H), 2.00 (s, 2H), 1.45 (s, 9H), 0.13 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 154.7, 144.0, 135.1, 127.7, (q, J = 32 Hz), (q, J = 4 Hz), (q, J = 270 Hz), (q, J = 4 Hz), 80.6, 34.9, 28.3 (3C), 19.4, -2.8 (2C); IR (neat) : υ 2976, 1695, 1319, 1120, 826, 743, 615 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 23 NO 2 F 3 Si), meas ; mp : 80 C. From the halogenoaryl 15 (860 mg, 1.87 mmol), following the general procedure D, the silylated compound 25b was obtained as a colorless oil (51 mg, 8%). Rf (5% diethyl ether/pentane): 0.41; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.62 (br s, 1H), 7.51 (d, J = 8.6 Hz, 1H), 7.46 (d, J = 8.6 Hz, 1H), (m, 2H), 1.48 (s, 9H), (m, 2H), 0.29 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 153.8, 151.7, 131.5, (q, J = 4 Hz), (q, J = 32 Hz), 126.2, (q, J = 3Hz), (J = 270 Hz), 81.1, 44.9, 28.4 (3C), 13.7, -1.2 (2C); IR (neat) : υ 2973, 1697, 1118, 812 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 23 NO 2 F 3 Si), meas tert-butyl 6-fluoro-3,3-dimethyl-3,4-dihydrobenzo[e][1,3]azasiline-1(2H)-carboxylate 26a tert-butyl 6-fluoro-4,4-dimethyl-3,4-dihydrobenzo[b][1,4]azasiline-1(2H)-carboxylate 26b F Si N Boc 26a C 15 H 22 FNO 2 Si MW = g/mol From the halogenoaryl 16 (483 mg, 1.17 mmol), following the general procedure C, the silylated compound 26a was obtained as a white solid (131 mg, 38%). From the halogenoaryl 16 (180 mg, 0.44 mmol), following the general procedure D, the silylated compound 26a was obtained as a white solid (94 mg, 72%). Rf (5% diethyl ether/pentane): 0.34; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.09 (br s, 1H), (m, 2H), 3.04 (br s, 2H), 1.92 (s, 2H), 1.43 (s, 9H), 0.11 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = (d, J = 242 Hz), 155.1, (d, J = 3 Hz), (d, J = 8 Hz), (d, J = 8 Hz), (d, J = 22 Hz), (d, J = 22 Hz), 80.1, 35.1, 28.4 (3C), 19.6, -2.7 (2C); IR (neat) : υ 2969, 2892, 1686, 1364, 1157, 836, 460 cm -1 ; HRMS (ESI+): theor (calc. for C 15 H 22 NO 2 FNaSi), meas ; mp : 66 C. - S17 -

18 From the halogenoaryl 16 (483 mg, 1.17 mmol), following the general procedure C, the silylated compound 26b was obtained as a colorless oil (31 mg, 9%). From the halogenoaryl 16 (180 mg, 0.44 mmol), following the general procedure D, the silylated compound 26b was obtained as a colorless oil (13 mg, 10%). Rf (5% diethyl ether/pentane): 0.46; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.29 (br s, 1H), 7.05 (dd, J = 7.8, 3.0 Hz, 1H), 6.96 (ddd, J = 8.7, 8.4, 3.0 Hz, 1H), (m, 2H), 1.46 (s, 9H), (m, 2H), 0.26 (s, 6H); 13 C NMR (50 MHz, CDCl 3 ) δ = (d, J = 245 Hz), 154.3, (d, J = 3Hz), (d, J = 5 Hz), (d, J = 7 Hz), (d, J = 20 Hz), (d, J = 22 Hz), 80.5, 45.1, 28.5 (3C), 13.6, -1.3 (2C); IR (neat) : υ 2973, 1699, 1362, 1141, 837 cm -1 ; HRMS (ESI+): theor (calc. for C 15 H 23 NO 2 FSi), meas tert-butyl 6-methoxy-3,3-dimethyl-3,4-dihydrobenzo[e][1,3]azasiline-1(2H)-carboxylate 27a tert-butyl 6-methoxy-4,4-dimethyl-3,4-dihydrobenzo[b][1,4]azasiline-1(2H)-carboxylate 27b From the halogenoaryl 17 (813 mg, 1.92 mmol), following the general procedure D, the silylated compound 27a was obtained as an oil (280 mg, 48%). Rf (5% diethyl ether/pentane): 0.17; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.05 (br s, 1H), (m, 2H), 3.79 (s, 3H), 3.04 (br s, 2H), 1.91 (s, 2H), 1.43 (s, 9H), 0.10 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 157.3, 155.3, 135.5, 134.1, 128.1, 114.6, 110.7, 79.7, 55.3, 35.4, 28.5 (3C), 19.7, -2.6 (2C); IR (neat) : υ 2969, 2899, 2839, 1684, 1363, 1157, 840 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 26 NO 3 Si), meas From the halogenoaryl 17 (813 mg, 1.92 mmol), following the general procedure D, the silylated compound 27b was obtained as an oil (181 mg, 31%). Rf (5% diethyl ether/pentane): 0.25; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.24 (d, J = 8.7 Hz, 1H), 6.90 (d, J = 3.0 Hz, 1H), 6.84 (dd, J = 8.7, 3.0 Hz, 1H), 3.80 (s, 3H), (m, 2H), 1.46 (s, 9H), S18 -

19 1.11 (m, 2H), 0.25 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 156.4, 154.4, 141.8, 132.1, 127.3, 117.8, 114.6, 80.0, 55.3, 45.0, 28.4 (3C), 13.7, -1.2 (2C); IR (neat) : υ 2953, 2899, 2834, 1690, 1150, 828 cm- 1 ; HRMS (ESI+): theor (calc. for C 16 H 26 NO 3 Si), meas tert-butyl 7-methoxy-3,3-dimethyl-3,4-dihydrobenzo[e][1,3]azasiline-1(2H)-carboxylate 28a tert-butyl 7-methoxy-4,4-dimethyl-3,4-dihydrobenzo[b][1,4]azasiline-1(2H)-carboxylate 28b From the halogenoaryl 18 (262 mg, 0.62 mmol), following the general procedure D, the silylated compound 28a was obtained as a colorless oil (25 mg, 13%). Rf (10% diethyl ether/pentane): 0.19; 1 H NMR (300 MHz, CDCl 3 ) δ = 6.98 (d, J = 8.4 Hz, 1H), 6.75 (br s, 1H), 6.65 (dd, J = 8.4, 2.4 Hz, 1H), 3.76 (s, 3H), 3.03 (br s, 2H), 1.86 (s, 2H), 1.45 (s, 9H), 0.09 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 157.4, 155.1, 141.7, 130.5, 126.1, 112.9, 112.2, 80.1, 55.5, 35.5, 28.6 (3C), 18.0, -2.6 (2C); IR (neat) : υ 2971, 1688, 1363, 1158, 831 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 26 NO 3 Si), meas MeO Si N Boc 28b C 16 H 25 NO 3 Si MW = g/mol From the halogenoaryl 18 (262 mg, 0.62 mmol), following the general procedure D, the silylated compound 28b was obtained as a colorless oil (114 mg, 60%). Rf (10% diethyl ether/pentane): 0.30; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.30 (d, J = 9.1 Hz, 1H), 6.92 (d, J = 2.1 Hz, 1H), 6.74 (dd, J = 9.1, 2.1 Hz, 1H), (m, 5H), 1.48 (s, 9H), (m, 2H), 0.23 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 160.3, 154.0, 150.1, 134.5, 121.7, 111.8, 111.4, 80.3, 55.2, 45.3, 28.5 (3C), 13.8, -0.9 (2C); IR (neat) : υ 2991, 2947, 2898, 1690, 1596, 1146, 833 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 26 NO 3 Si), meas S19 -

20 tert-butyl 7-(dimethylamino)-3,3-dimethyl-3,4-dihydrobenzo[e][1,3]azasiline-1(2H)-carboxylate 29a tert-butyl 7-(dimethylamino)-4,4-dimethyl-3,4-dihydrobenzo[b][1,4]azasiline-1(2H)-carboxylate 29b N Si N Boc 29a C 17 H 28 N 2 O 2 Si MW = g/mol From the halogenoaryl 19 (250 mg, 0.57 mmol), following the general procedure D, the silylated compound 29a was obtained as a colorless oil (18 mg, 10%). Rf (10% diethyl ether/pentane): 0.12; 1 H NMR (300 MHz, CDCl 3 ) δ = 6.95 (d, J = 8.3 Hz, 1H), (m, 1H), 6.53 (dd, J = 8.3, 2.7 Hz, 1H), 3.04 (br s, 2H), 2.88 (s, 6H), 1.82 (s, 2H), 1.45 (s, 9H), (s, 6H); 13 C NMR (50 MHz, CDCl 3 ) δ = 155.1, 149.0, 141.5, 130.2, 122.2, 111.3, 110.8, 79.7, 41.1 (2C), 35.6, 28.5 (3C), 17.5, -2.6 (2C); IR (neat) : υ 2971, 2883, 2796, 1687, 1363, 1161, 828 cm -1 ; HRMS (ESI+): theor (calc. for C 17 H 29 N 2 O 2 Si), meas From the halogenoaryl 19 (250 mg, 0.57 mmol), following the general procedure D, the silylated compound 29b was obtained as a colorless oil (150 mg, 82%). Rf (10% diethyl ether/pentane): 0.23; 1 H NMR (200 MHz, CDCl 3 ) δ = 7.25 (d, J = 8.2 Hz, 1H), 6.71 (d, J = 2.4 Hz, 1H), 6.57 (dd, J = 8.2, 2.4 Hz, 1H), (m, 2H), 2.94 (s, 6H), 1.48 (s, 9H), (m, 2H), 0.21 (s, 6H); 13 C NMR (50 MHz, CDCl 3 ) δ = 154.1, 151.2, 149.7, 134.1, 116.3, 110.2, 109.7, 79.8, 45.2, 40.2 (2C), 28.4 (3C), 13.8, -0.9 (2C); IR (neat) : υ 2985, 2893, 2801, 1691, 1378, 1147, 1081, 831 cm -1 ; HRMS (ESI+): theor (calc. for C 17 H 29 N 2 O 2 Si), meas tert-butyl 3,3,6-trimethyl-3,4-dihydrobenzo[e][1,3]azasiline-1(2H)-carboxylate 30a tert-butyl 4,4,6-trimethyl-3,4-dihydrobenzo[b][1,4]azasiline-1(2H)-carboxylate 30b Si N Boc 30a C 16 H 25 NO 2 Si MW = g/mol From the halogenoaryl 20 (710 mg, 1.74 mmol), following the general procedure D, the silylated compound 30a was obtained as a white solid (198 mg, 39%). - S20 -

21 Rf (5% diethyl ether/pentane): 0.25; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.02 (br s, 1H), (m, 2H), 3.04 (br s, 2H), 2.28 (s, 3H), 1.89 (s, 2H), 1.43 (s, 9H), 0.10 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 155.1, 138.2, 135.2, 133.6, 130.4, 126.8, 125.9, 79.7, 34.9, 28.4 (3C), 20.9, 19.0, -2.7 (2C); IR (neat) : υ 2963, 2922, 2870, 1683, 1158, 826 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 26 NO 2 Si), meas ; mp : 71 C. Si C 16 H 25 NO 2 Si N MW = g/mol Boc 30b From the halogenoaryl 20 (710 mg, 1.74 mmol), following the general procedure D, the silylated compound 30b was obtained as a colorless oil (256 mg, 50%). Rf (5% diethyl ether/pentane): 0.41; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.28 (d, J = 8.4 Hz, 1H), 7.26 (d, J = 1.2 Hz, 1H), 7.15 (dd, J = 8.4, 1.2 Hz, 1H), (m, 2H), 2.37 (s, 3H), 1.53 (s, 9H), (2H), 0.31 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 154.1, 146.0, 133.8, 133.7, 130.2, 129.7, 125.6, 79.9, 44.8, 28.3 (3C), 20.8, 13.7, -1.3 (2C); IR (neat) : υ 2974, 2893, 1694, 1364, 1149, 821 cm - 1 ; HRMS (ESI+): theor (calc. for C 16 H 26 NO 2 Si), meas tert-butyl 3,3,7-trimethyl-3,4-dihydrobenzo[e][1,3]azasiline-1(2H)-carboxylate 31a tert-butyl 4,4,7-trimethyl-3,4-dihydrobenzo[b][1,4]azasiline-1(2H)-carboxylate 31b From the halogenoaryl 21 (305 mg, 0.75 mmol), following the general procedure D, the silylated compound 31a was obtained as a colorless oil (71 mg, 33%). Rf (5% diethyl ether/pentane): 0.28; 1 H NMR (300 MHz, CDCl 3 ) δ = 6.97 (d, J = 7.5 Hz, 1H), 6.96 (d, J = 1.2 Hz, 1H), 6.86 (dd, J = 7.5, 1.2 Hz, 1H), 3.04 (br s, 2H), 2.29 (s, 3H), 1.89 (s, 2H), 1.45 (s, 9H), 0.01 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 155.0, 140.6, 134.7, 130.7, 129.7, 127.7, 126.5, 79.7, 35.2, 28.3 (3C), 20.9, 18.4, -2.7 (2C). IR (neat) : υ 2970, 2920, 1692, 1150, 830 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 26 NO 2 Si), meas From the halogenoaryl 21 (305 mg, 0.75 mmol), following the general procedure D, the silylated compound 31b was obtained as a colorless oil (132 mg, 60%). - S21 -

22 Rf (5% diethyl ether/pentane): 0.44; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.32 (d, J = 7.2 Hz, 1H), 7.22 (br s, 1H), 6.99 (d, J = 7.2 Hz, 1H), (m, 2H), 2.35 (s, 3H), 1.51 (s, 9H), (m, 2H), 0.27 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 154.0, 148.5, 138.9, 133.3, 126.8, 126.4, 125.6, 79.9, 44.9, 28.3 (3C), 21.4, 13.7, -1.2 (2C); IR (neat) : υ 2974, 2899, 1694, 1146, 833 cm -1 ; HRMS (ESI+): theor (calc. for C 16 H 26 NO 2 Si), meas Allyl 3,3-dimethyl-3,4-dihydrobenzo[e][1,3]azasiline-1(2H)-carboxylate 35a Allyl 4,4-dimethyl-3,4-dihydrobenzo[b][1,4]azasiline-1(2H)-carboxylate 35b Si N Alloc 35a C 14 H 19 NO 2 Si MW = g/mol From the halogenoaryl 32 (529 mg, 1.25 mmol), following the general procedure C, the silylated compound 35a was obtained as a colorless oil (89 mg, 34%). Rf (5% diethyl ether/pentane): 0.40; 1 H NMR (300 MHz, CDCl 3 ) δ = (m, 4H), (m, 1H), (m, 2H), 4.62 (d, J = 4.6 Hz, 2H), 3.14 (br s, 2H), 1.96 (s, 2H), 0.11 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 155.6, 140.2, 134.4, 133.0, 130.1, 127.2, 126.4, 125.6, 117.2, 66.3, 35.9, 19.2, -2.7 (2C); IR (neat) : υ 2948, 2880, 1694, 1250, 840, 758 cm -1 ; HRMS (ESI+): theor (calc. for C 14 H 20 NO 2 Si), meas From the halogenoaryl 32 (529 mg, 1.25 mmol), following the general procedure C, the silylated compound 35b was obtained as a colorless oil (93 mg, 36%). Rf (5% diethyl ether/pentane): 0.27; 1 H NMR (300 MHz, CDCl 3 ) δ = (m, 3H), (m, 1H), 5.81 (ddt, J = 17.2, 10.5, 5.4 Hz, 1H), 5.15 (d, J = 17.2 Hz, 2H), 5.06 (d, J = 10.5 Hz, 1H), 4.52 (d, J = 5.4 Hz, 1H), (m, 2H), (m, 2H), 0.13 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 154.8, 148.1, 133.7, 133.0, 130.9, 129.3, 125.8, 125.2, 117.5, 66.3, 45.4, 14.0, -1.1 (2C); IR (neat) : υ 2953, 2894, 1699, 1388, 1264, 833, 768, 456 cm -1 ; HRMS (ESI+): theor (calc. for C 14 H 20 NO 2 Si), meas ,4-dimethyl-1-tosyl-1,2,3,4-tetrahydrobenzo[b][1,4]azasiline 36b - S22 -

23 From the halogenoaryl 33 (764 mg, 1.55 mmol), following the general procedure C, the silylated compound 36b was obtained as a yellow solid (326 mg, 63%). Rf (10% diethyl ether/pentane): 0.36; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.63 (dd, J = 8.4, 1.5 Hz, 1H), 7.43 (d, J = 6.6 Hz, 2H), (m, 2H), 7.21 (m, 1H), 7.16 (d, J = 6.6 Hz, 2H), (m, 2H), 2.36 (s, 3H), (m, 2H), (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 146.4, 143.3, 138.4, 134.3, 132.0, 129.8, 129.5, 127.5, 126.9, 126.1, 47.8, 21.5, 12.0, -1.5 (2C); IR (neat) : υ 2931, 1338, 1151, 670 cm -1 ; HRMS (ESI+): theor (calc. for C 17 H 22 NO 2 SiS), meas ; mp : 90 C 3,3-dimethyl-1-(methylsulfonyl)-1,2,3,4-tetrahydrobenzo[e][1,3]azasiline 37a 4,4-dimethyl-1-(methylsulfonyl)-1,2,3,4-tetrahydrobenzo[b][1,4]azasiline 37b Sulfonamide 42 From the halogenoaryl 34 (520 mg, 1.24 mmol), following the general procedure C, the silylated compound 37a was obtained as a yellow solid (28 mg, 9%). Rf (50% diethyl ether/pentane): 0.62; 1 H NMR (300 MHz, CDCl 3 ) δ = (m, 1H), (m, 3H), 2.98 (s, 3H), 2.97 (s, 2H), 1.98 (s, 2H), 0.06 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 137.8, 134.2, 129.5, 125.9, 125.3, 125.0, 38.4, 35.8, 18.3, -3.9 (2C); IR (neat) : υ 3064, 2949, 1326, 1145, 825 cm -1 ; HRMS (ESI+): theor (calc. for C 11 H 18 NO 2 SiS), meas ; mp : 62 C. Si N Ms 37b C 11 H 17 NO 2 SSi MW = g/mol From the halogenoaryl 34 (520 mg, 1.24 mmol), following the general procedure C, the silylated compound 37b was obtained as a yellow solid (61 mg, 19%). Rf (50% diethyl ether/pentane): 0.77; 1 H NMR (300 MHz, CDCl 3 ) δ = (m, 2H), (m, 1H), (m, 1H), (m, 2H), 2.92 (s, 3H), (m, 2H), 0.31 (s, 6H); 13 C NMR (50 MHz, CDCl 3 ) δ = 146.5, 134.7, 131.2, 130.1, 126.1, 125.6, 47.3, 41.0, 13.5, -0.9 (2C); IR (neat) : υ 2948, 2902, 1339, 1148, 776 cm -1 ; HRMS (ESI+): theor (calc. for C 11 H 18 NO 2 SiS), meas ; mp : 55 C. 42 O I N S O Si C 11 H 16 INO 2 SSi MW = g/mol - S23 -

24 From the halogenoaryl 34 (520 mg, 1.2 mmol), following the general procedure C, the sulfonamide 42 was obtained as a colorless oil (75 mg, 16%). Rf (50% diethyl ether/pentane): 0.72; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.80 (dd, J = 7.9, 1.1 Hz, 1H), 7.42 (dd, J = 7.9, 1.4 Hz, 1H), 7.31 (ddd, J = 7.9, 7.6, 1.1 Hz, 1H), 6.94 (ddd, J = 7.9, 7.6, 1.4 Hz, 1H), (m, 2H), 3.38 (A of AB quartet, J = 13.9 Hz, 1H), 2.70 (B of AB quartet, J = 13.9 Hz, 1H), (m, 1H), (m, 1H), 0.39 (s, 3H), 0.13 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ = 145.7, 139.8, (2C), 128.2, 101.8, 49.8, 46.0, 11.1, -2.8, -3.8; IR (neat) : υ 2951, 2725, 2489, 1591, 1524, 1091, 811, 795 cm -1 ; HRMS (ESI+): theor (calc. for C 11 H 17 NO 2 SiSI), meas Supplementary methods: Details synthetic procedures for the rearrangement study (chloromethyl)(2-iodophenoxy)dimethylsilane 43 A mixture of 2-iodophenol (6.6 g, 30 mmol, 1 equiv.) and chloromethyldimethylchlorosilane (8.59 g, 60 mmol, 2.0 equiv.) was heated neat at 130 C under reflux. After 48h, the reaction mixture was distillated under reduced pressure to afford 43 as a colorless oil (7.6 g, 73%). Rf (pentane): 0.45; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.76 (dd, J = 7.9, 1.6 Hz, 1H), 7.76 (ddd, J = 8.1, 7.6, 1.6 Hz, 1H), 6.87 (dd, J = 8.1, 1.4 Hz, 1H), 6.74 (ddd, J = 7.9, 7.6, 1.4 Hz, 1H), 3.00 (s, 2H), 0.45 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 154.3, 139.4, 129.5, 123.8, 119.3, 90.7, 29.4, -2.7 (2C); IR (neat) : υ 2957, 2899, 1469, 1234, 1017, 841, 745, 646 cm -1 ; HRMS (EI): theor (calc. for C 9 H 12 ClIOSi), meas ,3-dimethyl-2,3-dihydrobenzo[d][1,3]oxasilole 38 To a suspension of sodium (860 mg, 37.4 mmol, 2 equiv.) in toluene (60 ml) was added a solution of starting material 43 (6.11 g, 18.7 mmol, 1 equiv.) in toluene (10 ml) and the reaction mixture was heated under reflux. After 3.5 h, the reaction was cooled down to -40 C and quenched with a saturated aqueous solution of NaHPO 4 and extracted with diethyl ether. The resulting organic phase was washed with brine, dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The crude mixture was purified by flash chromatography on silica gel (1% diethyl ether/pentane) to give product 38 as a colorless oil (1.91 g, 62%). - S24 -

25 Rf (1% diethyl ether/pentane): 0.37; 1 H NMR (300 MHz, CDCl 3 ) δ = 7.46 (dd, J = 7.2, 1.5 Hz, 1H), 7.29 (ddd, J = 8.3, 7.0, 1.5 Hz, 1H), 6.91 (ddd, J = 7.2, 8.3, 0.8 Hz, 1H), 6.86 (dd, J = 7.0, 0.8Hz, 1H), 3.91 (s, 2H), 0.41 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ = 168.4, 132.6, 131.7, 120.5, 120.1, 112.7, 62.0, -2.0 (2C); IR (neat) : υ 2957, 2899, 1591, 1442, 1183, 802, 755 cm -1 ; HRMS (EI): theor (calc. for C 9 H 12 OSi), meas Procedure for the ring expansion To a solution of 5-membered ring 38 (164 mg, 1.0 mmol, 1.0 equiv.) in anhydrous THF (5 ml) was added iodochloromethane (265 mg, 1.5 mmol, 1.5 equiv.). The reaction mixture was cooled down to C and MeLi.LiBr (1.5M in hexane, 1.33 ml, 2.0 mmol, 2.0 equiv.) was added dropwise. The medium was allowed to warm up to -78 C and maintained at this temperature for 1h. The reaction mixture was then quenched with a saturated aqueous solution of NH 4 Cl, warmed up to room temperature and extracted with diethyl ether, washed with brine, dried over Na 2 SO 4 and concentrated over reduced pressure. The crude mixture was purified by flash chromatography on silica gel (pentane) to give 6-membered rings 5a and 5b as colorless oils (82 mg, 46%). - S25 -

26 6. Supplementary figures: Plot of log (b/a) against Hammett constants ( ) Hammett constants are literature data, measured in aqueous solution for para- and meta-substituted benzoic acid. 9 entry R Hammett constant ( ) ratio (b/a) Log (b/a) 1 5-CF / CF / F / Cl / OMe / F / H 0 55/ CH / CH / OMe / NMe / log (b/a) 2 1,5 1 0,5 0-0,5-1 -1,5 5-NMe 2 R 2 = 0,940 5-OMe 4-Me H 5-Me 4-OMe 5-F 4-F 5-Cl 5-CF 3 4-CF ,2-0,7-0,2 0,3 0,8 σ 9 Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, S26 -

27 7. Supplementary figures: 1 H and 13 C NMR spectra tert-butyl ((chloromethyl)dimethylsilyl)methyl(2-iodophenyl)carbamate 6 I N Si Cl Boc - S27 -

28 (chloromethyl)((2-iodophenoxy)methyl)dimethylsilane 7 - S28 -

29 tert-butyl 2-bromo-5-(trifluoromethyl)phenyl(((chloromethyl)dimethylsilyl)methyl)carbamate 12 - S29 -

A facile and general route to 3-((trifluoromethyl)thio)benzofurans and 3-((trifluoromethyl)thio)benzothiophenes

A facile and general route to 3-((trifluoromethyl)thio)benzofurans and 3-((trifluoromethyl)thio)benzothiophenes Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 A facile and general route to 3-((trifluoromethyl)thio)benzofurans and 3-((trifluoromethyl)thio)benzothiophenes

Διαβάστε περισσότερα

Direct Transformation of Ethylarenes into Primary Aromatic Amides with N-Bromosuccinimide and I 2 -aq NH 3

Direct Transformation of Ethylarenes into Primary Aromatic Amides with N-Bromosuccinimide and I 2 -aq NH 3 Supporting Information Direct Transformation of Ethylarenes into Primary Aromatic Amides with N-Bromosuccinimide and I 2 -aq NH 3 Shohei Shimokawa, Yuhsuke Kawagoe, Katsuhiko Moriyama, Hideo Togo* Graduate

Διαβάστε περισσότερα

Supporting Information

Supporting Information Supporting Information Montmorillonite KSF-Catalyzed One-pot, Three-component, Aza-Diels- Alder Reactions of Methylenecyclopropanes With Arylaldehydes and Aromatic Amines Li-Xiong Shao and Min Shi* General

Διαβάστε περισσότερα

Supporting Information

Supporting Information Supporting Information for Lewis acid-catalyzed redox-neutral amination of 2-(3-pyrroline-1-yl)benzaldehydes via intramolecular [1,5]-hydride shift/isomerization reaction Chun-Huan Jiang, Xiantao Lei,

Διαβάστε περισσότερα

Supporting Information

Supporting Information Supporting Information Lewis acid catalyzed ring-opening reactions of methylenecyclopropanes with diphenylphosphine oxide in the presence of sulfur or selenium Min Shi,* Min Jiang and Le-Ping Liu State

Διαβάστε περισσότερα

Copper-catalyzed formal O-H insertion reaction of α-diazo-1,3-dicarb- onyl compounds to carboxylic acids with the assistance of isocyanide

Copper-catalyzed formal O-H insertion reaction of α-diazo-1,3-dicarb- onyl compounds to carboxylic acids with the assistance of isocyanide Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Copper-catalyzed formal O-H insertion reaction of α-diazo-1,3-dicarb- onyl compounds to carboxylic

Διαβάστε περισσότερα

Supporting Information

Supporting Information Supporting Information Ceric Ammonium Nitrate (CAN) catalyzed efficient one-pot three component aza-diels-alder reactions for a facile synthesis of tetrahydropyranoquinoline derivatives Ravinder Goud Puligoundla

Διαβάστε περισσότερα

Hiyama Cross-Coupling of Chloro-, Fluoroand Methoxy- pyridyl trimethylsilanes : Room-temperature Novel Access to Functional Bi(het)aryl

Hiyama Cross-Coupling of Chloro-, Fluoroand Methoxy- pyridyl trimethylsilanes : Room-temperature Novel Access to Functional Bi(het)aryl Hiyama Cross-Coupling of Chloro-, Fluoroand Methoxy- pyridyl trimethylsilanes : Room-temperature Novel Access to Functional Bi(het)aryl Philippe Pierrat, Philippe Gros* and Yves Fort Synthèse Organométallique

Διαβάστε περισσότερα

Facile construction of the functionalized 4H-chromene via tandem. benzylation and cyclization. Jinmin Fan and Zhiyong Wang*

Facile construction of the functionalized 4H-chromene via tandem. benzylation and cyclization. Jinmin Fan and Zhiyong Wang* Facile construction of the functionalized 4H-chromene via tandem benzylation and cyclization Jinmin Fan and Zhiyong Wang* Hefei National Laboratory for Physical Science at Microscale, Joint- Lab of Green

Διαβάστε περισσότερα

Supporting Information. Table of Contents. II. Experimental procedures. II. Copies of 1H and 13C NMR spectra for all compounds

Supporting Information. Table of Contents. II. Experimental procedures. II. Copies of 1H and 13C NMR spectra for all compounds Electronic upplementary Material (EI) for rganic & Biomolecular Chemistry. This journal is The Royal ociety of Chemistry 2017 Laboratoire de Méthodologie et ynthèse de Produit aturels. Université du Québec

Διαβάστε περισσότερα

Supporting Information

Supporting Information Supporting Information Copper/Silver Cocatalyzed Oxidative Coupling of Vinylarenes with ICH 2 CF 3 or ICH 2 CHF 2 Leading to β-cf 3 /CHF 2 -Substituted Ketones Niannian Yi, Hao Zhang, Chonghui Xu, Wei

Διαβάστε περισσότερα

Site-Selective Suzuki-Miyaura Cross-Coupling Reactions of 2,3,4,5-Tetrabromofuran

Site-Selective Suzuki-Miyaura Cross-Coupling Reactions of 2,3,4,5-Tetrabromofuran 1 Site-Selective Suzuki-Miyaura Cross-Coupling Reactions of 2,3,4,5-Tetrabromofuran Munawar Hussain, a Rasheed Ahmad Khera, a Nguyen Thai Hung, a Peter Langer* a,b a Institut für Chemie, Universität Rostock,

Διαβάστε περισσότερα

Supporting Information

Supporting Information Supporting Information for AgOTf-catalyzed one-pot reactions of 2-alkynylbenzaldoximes with α,β-unsaturated carbonyl compounds Qiuping Ding 1, Dan Wang 1, Puying Luo* 2, Meiling Liu 1, Shouzhi Pu* 3 and

Διαβάστε περισσότερα

Vilsmeier Haack reagent-promoted formyloxylation of α-chloro-narylacetamides

Vilsmeier Haack reagent-promoted formyloxylation of α-chloro-narylacetamides Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 205 Vilsmeier aack reagent-promoted formyloxylation of α-chloro-arylacetamides by formamide Jiann-Jyh

Διαβάστε περισσότερα

Electronic Supplementary Information (ESI)

Electronic Supplementary Information (ESI) Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry Electronic Supplementary Information (ESI) For Iron-Catalysed xidative Amidation of Alcohols with Amines Silvia Gaspa, a Andrea

Διαβάστε περισσότερα

Supporting information

Supporting information Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2014 Supporting information Copper-catalysed intramolecular O-arylation: a simple

Διαβάστε περισσότερα

Supporting Information. Synthesis and biological evaluation of 2,3-Bis(het)aryl-4-azaindoles Derivatives as protein kinases inhibitors

Supporting Information. Synthesis and biological evaluation of 2,3-Bis(het)aryl-4-azaindoles Derivatives as protein kinases inhibitors Supporting Information Synthesis and biological evaluation of 2,3-Bis(het)aryl-4-azaindoles Derivatives as protein kinases inhibitors Frédéric Pin, a Frédéric Buron, a Fabienne Saab, a Lionel Colliandre,

Διαβάστε περισσότερα

Electronic Supplementary Information

Electronic Supplementary Information Electronic Supplementary Information Unprecedented Carbon-Carbon Bond Cleavage in Nucleophilic Aziridine Ring Opening Reaction, Efficient Ring Transformation of Aziridines to Imidazolidin-4-ones Jin-Yuan

Διαβάστε περισσότερα

Supporting information

Supporting information Electronic upplementary Material (EI) for New Journal of Chemistry. This journal is The Royal ociety of Chemistry and the Centre National de la Recherche cientifique 7 upporting information Lipase catalyzed,-addition

Διαβάστε περισσότερα

and Selective Allylic Reduction of Allylic Alcohols and Their Derivatives with Benzyl Alcohol

and Selective Allylic Reduction of Allylic Alcohols and Their Derivatives with Benzyl Alcohol FeCl 3 6H 2 O-Catalyzed Disproportionation of Allylic Alcohols and Selective Allylic Reduction of Allylic Alcohols and Their Derivatives with Benzyl Alcohol Jialiang Wang, Wen Huang, Zhengxing Zhang, Xu

Διαβάστε περισσότερα

Divergent synthesis of various iminocyclitols from D-ribose

Divergent synthesis of various iminocyclitols from D-ribose Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 205 Divergent synthesis of various iminocyclitols from D-ribose Ramu Petakamsetty,

Διαβάστε περισσότερα

Metal-free Oxidative Coupling of Amines with Sodium Sulfinates: A Mild Access to Sulfonamides

Metal-free Oxidative Coupling of Amines with Sodium Sulfinates: A Mild Access to Sulfonamides Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2014 Supporting information for Metal-free Oxidative Coupling of Amines with Sodium Sulfinates:

Διαβάστε περισσότερα

Room Temperature Highly Diastereoselective Zn-Mediated. Allylation of Chiral N-tert-Butanesulfinyl Imines: Remarkable Reaction Condition Controlled

Room Temperature Highly Diastereoselective Zn-Mediated. Allylation of Chiral N-tert-Butanesulfinyl Imines: Remarkable Reaction Condition Controlled Supporting Information for: Room Temperature Highly Diastereoselective Zn-Mediated Allylation of Chiral N-tert-Butanesulfinyl Imines: Remarkable Reaction Condition Controlled Stereoselectivity Reversal

Διαβάστε περισσότερα

Supporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2006

Supporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2006 Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2006 1 A Facile Way to Synthesize 2H-Chromenes: Reconsideration of the Reaction Mechanism between Salicylic Aldehyde and

Διαβάστε περισσότερα

Supporting Information. Asymmetric Binary-acid Catalysis with Chiral. Phosphoric Acid and MgF 2 : Catalytic

Supporting Information. Asymmetric Binary-acid Catalysis with Chiral. Phosphoric Acid and MgF 2 : Catalytic Supporting Information Asymmetric Binary-acid Catalysis with Chiral Phosphoric Acid and MgF 2 : Catalytic Enantioselective Friedel-Crafts Reactions of β,γ- Unsaturated-α-Ketoesters Jian Lv, Xin Li, Long

Διαβάστε περισσότερα

Supplementary information

Supplementary information Electronic Supplementary Material (ESI) for MedChemComm. This journal is The Royal Society of Chemistry 2015 Supplementary information Synthesis of carboxyimidamide-substituted benzo[c][1,2,5]oxadiazoles

Διαβάστε περισσότερα

First DMAP-mediated direct conversion of Morita Baylis. Hillman alcohols into γ-ketoallylphosphonates: Synthesis of

First DMAP-mediated direct conversion of Morita Baylis. Hillman alcohols into γ-ketoallylphosphonates: Synthesis of Supporting Information File 1 for First DMAP-mediated direct conversion of Morita Baylis Hillman alcohols into γ-ketoallylphosphonates: Synthesis of γ-aminoallylphosphonates Marwa Ayadi 1,2, Haitham Elleuch

Διαβάστε περισσότερα

Fluorinative Ring-opening of Cyclopropanes by Hypervalent Iodine Reagents. An Efficient Method for 1,3- Oxyfluorination and 1,3-Difluorination

Fluorinative Ring-opening of Cyclopropanes by Hypervalent Iodine Reagents. An Efficient Method for 1,3- Oxyfluorination and 1,3-Difluorination Electronic Supplementary Material (ESI) for Chemical Science. This journal is The Royal Society of Chemistry 2016 Supporting Information Fluorinative Ring-opening of Cyclopropanes by Hypervalent Iodine

Διαβάστε περισσότερα

Supporting Information. Experimental section

Supporting Information. Experimental section Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2014 Supporting Information Experimental section General. Anhydrous solvents were transferred by

Διαβάστε περισσότερα

Copper-Catalyzed Oxidative Dehydrogenative N-N Bond. Formation for the Synthesis of N,N -Diarylindazol-3-ones

Copper-Catalyzed Oxidative Dehydrogenative N-N Bond. Formation for the Synthesis of N,N -Diarylindazol-3-ones Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers. This journal is the Partner Organisations 2016 Supporting information Copper-Catalyzed Oxidative Dehydrogenative - Bond Formation

Διαβάστε περισσότερα

Supporting Information One-Pot Approach to Chiral Chromenes via Enantioselective Organocatalytic Domino Oxa-Michael-Aldol Reaction

Supporting Information One-Pot Approach to Chiral Chromenes via Enantioselective Organocatalytic Domino Oxa-Michael-Aldol Reaction Supporting Information ne-pot Approach to Chiral Chromenes via Enantioselective rganocatalytic Domino xa-michael-aldol Reaction Hao Li, Jian Wang, Timiyin E-Nunu, Liansuo Zu, Wei Jiang, Shaohua Wei, *

Διαβάστε περισσότερα

Supporting Information

Supporting Information Electronic upplementary Material (EI) for Green Chemistry. This journal is The Royal ociety of Chemistry 204 upporting Information ynthesis of sulfonamides via I 2 -mediated reaction of sodium sulfinates

Διαβάστε περισσότερα

Highly enantioselective cascade synthesis of spiropyrazolones. Supporting Information. NMR spectra and HPLC traces

Highly enantioselective cascade synthesis of spiropyrazolones. Supporting Information. NMR spectra and HPLC traces Highly enantioselective cascade synthesis of spiropyrazolones Alex Zea a, Andrea-Nekane R. Alba a, Andrea Mazzanti b, Albert Moyano a and Ramon Rios a,c * Supporting Information NMR spectra and HPLC traces

Διαβάστε περισσότερα

First Total Synthesis of Antimitotic Compound, (+)-Phomopsidin

First Total Synthesis of Antimitotic Compound, (+)-Phomopsidin First Total Synthesis of Antimitotic Compound, (+)-Phomopsidin Takahiro Suzuki, a Kenji Usui, a Yoshiharu Miyake, a Michio Namikoshi, b and Masahisa Nakada a, * a Department of Chemistry, School of Science

Διαβάστε περισσότερα

The Free Internet Journal for Organic Chemistry

The Free Internet Journal for Organic Chemistry The Free Internet Journal for Organic Chemistry Paper Archive for Organic Chemistry Arkivoc 2018, part iii, S1-S6 Synthesis of dihydropyranones and dihydropyrano[2,3- d][1,3]dioxine-diones by cyclization

Διαβάστε περισσότερα

Rh(III)-Catalyzed C-H Amidation with N-hydroxycarbamates: A. new Entry to N-Carbamate Protected Arylamines

Rh(III)-Catalyzed C-H Amidation with N-hydroxycarbamates: A. new Entry to N-Carbamate Protected Arylamines Rh(III)-Catalyzed C-H Amidation with N-hydroxycarbamates: A new Entry to N-Carbamate Protected Arylamines Bing Zhou,* Juanjuan Du, Yaxi Yang,* Huijin Feng, Yuanchao Li Shanghai Institute of Materia Medica,

Διαβάστε περισσότερα

Eco-friendly synthesis of diverse and valuable 2-pyridones by catalyst- and solvent-free thermal multicomponent domino reaction

Eco-friendly synthesis of diverse and valuable 2-pyridones by catalyst- and solvent-free thermal multicomponent domino reaction Electronic Supplementary Material (ESI) for Green Chemistry. This journal is The Royal Society of Chemistry 2015 SUPPRTIG IFRMATI Eco-friendly synthesis of diverse and valuable 2-pyridones by catalyst-

Διαβάστε περισσότερα

Enantioselective Organocatalytic Michael Addition of Isorhodanines. to α, β-unsaturated Aldehydes

Enantioselective Organocatalytic Michael Addition of Isorhodanines. to α, β-unsaturated Aldehydes Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2016 Enantioselective Organocatalytic Michael Addition of Isorhodanines to α,

Διαβάστε περισσότερα

Tributylphosphine-Catalyzed Cycloaddition of Aziridines with Carbon Disulfide and Isothiocyanate

Tributylphosphine-Catalyzed Cycloaddition of Aziridines with Carbon Disulfide and Isothiocyanate upporting Information Tributylphosphine-Catalyzed Cycloaddition of Aziridines with Carbon Disulfide and Isothiocyanate Jing-Yu Wu, Zhi-Bin Luo, Li-Xin Dai and Xue-Long Hou* a tate Key Laboratory of Organometallic

Διαβάστε περισσότερα

Supporting Information

Supporting Information Supporting Information Wiley-VC 007 9 Weinheim, Germany ew ear Infrared Dyes and Fluorophores Based on Diketopyrrolopyrroles Dipl.-Chem. Georg M. Fischer, Dipl.-Chem. Andreas P. Ehlers, Prof. Dr. Andreas

Διαβάστε περισσότερα

Regioselectivity in the Stille coupling reactions of 3,5- dibromo-2-pyrone.

Regioselectivity in the Stille coupling reactions of 3,5- dibromo-2-pyrone. Regioselectivity in the Stille coupling reactions of 3,5- dibromo-2-pyrone. Won-Suk Kim, Hyung-Jin Kim and Cheon-Gyu Cho Department of Chemistry, Hanyang University, Seoul 133-791, Korea Experimental Section

Διαβάστε περισσότερα

Aminofluorination of Fluorinated Alkenes

Aminofluorination of Fluorinated Alkenes Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2018 Synthesis of ɑ CF 3 and ɑ CF 2 H Amines via Aminofluorination of Fluorinated Alkenes Ling Yang,

Διαβάστε περισσότερα

SUPPORTING INFORMATION. Transition Metal-Free Arylations of In-Situ Generated Sulfenates with Diaryliodonium Salts

SUPPORTING INFORMATION. Transition Metal-Free Arylations of In-Situ Generated Sulfenates with Diaryliodonium Salts S1 SUPPORTING INFORMATION Transition Metal-Free Arylations of In-Situ Generated Sulfenates with Diaryliodonium Salts Hao Yu, Zhen Li, and Carsten Bolm* Institute of Organic Chemistry, RWTH Aachen University

Διαβάστε περισσότερα

Supporting Information. Experimental section

Supporting Information. Experimental section Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2014 Supporting Information Experimental section General. Proton nuclear magnetic resonance ( 1

Διαβάστε περισσότερα

Supporting Information for Iron-catalyzed decarboxylative alkenylation of cycloalkanes with arylvinylic carboxylic acids via a radical process

Supporting Information for Iron-catalyzed decarboxylative alkenylation of cycloalkanes with arylvinylic carboxylic acids via a radical process Supporting Information for Iron-catalyzed decarboxylative alkenylation of cycloalkanes with arylvinylic carboxylic acids via a radical process Jincan Zhao 1, Hong Fang 1, Jianlin Han* 1,2 and Yi Pan* 1

Διαβάστε περισσότερα

The N,S-Bidentate Ligand Assisted Pd-Catalyzed C(sp 2 )-H. Carbonylation using Langlois Reagent as CO Source. Supporting Information.

The N,S-Bidentate Ligand Assisted Pd-Catalyzed C(sp 2 )-H. Carbonylation using Langlois Reagent as CO Source. Supporting Information. Electronic upplementary Material (EI) for rganic & Biomolecular Chemistry. This journal is The Royal ociety of Chemistry 2018 The,-Bidentate Ligand Assisted Pd-Catalyzed C(sp 2 )-H Carbonylation using

Διαβάστε περισσότερα

Supporting Information for

Supporting Information for Supporting Information for An atom-economic route to densely functionalized thiophenes via base-catalyzed rearrangement of 5-propargyl-2H-thiopyran-4(3H)-ones Chunlin Tang a, Jian Qin b, Xingqi Li *a a

Διαβάστε περισσότερα

Efficient and Simple Zinc mediated Synthesis of 3 Amidoindoles

Efficient and Simple Zinc mediated Synthesis of 3 Amidoindoles Electronic Supplementary Material (ESI) for rganic and Biomolecular Chemistry SUPPRTIG IFRMATI Efficient and Simple Zinc mediated Synthesis of 3 Amidoindoles Anahit Pews-Davtyan and Matthias Beller* Leibniz-Institut

Διαβάστε περισσότερα

Pd Catalyzed Carbonylation for the Construction of Tertiary and

Pd Catalyzed Carbonylation for the Construction of Tertiary and Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2014 Pd Catalyzed Carbonylation for the Construction of Tertiary and Quaternary

Διαβάστε περισσότερα

Supplementary Data. Engineering, Nanjing University, Nanjing , P. R. China;

Supplementary Data. Engineering, Nanjing University, Nanjing , P. R. China; Supplementary Data Synthesis, Chemo-selective Properties of Substituted 9-Aryl-9H-fluorenes from Triarylcarbinols and Enantiomerical Kinetics of Chiral 9-Methoxy-11-(naphthalen-1-yl)-11H-benzo[a]fluorene

Διαβάστε περισσότερα

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for rganic Chemistry Frontiers. This journal is the Partner rganisations 2018 Palladium-catalyzed direct approach to α-cf 3 aryl ketones from arylboronic acids Bo

Διαβάστε περισσότερα

Direct Palladium-Catalyzed Arylations of Aryl Bromides. with 2/9-Substituted Pyrimido[5,4-b]indolizines

Direct Palladium-Catalyzed Arylations of Aryl Bromides. with 2/9-Substituted Pyrimido[5,4-b]indolizines Direct Palladium-Catalyzed Arylations of Aryl Bromides with 2/9-Substituted Pyrimido[5,4-b]indolizines Min Jiang, Ting Li, Linghua Meng, Chunhao Yang,* Yuyuan Xie*, and Jian Ding State Key Laboratory of

Διαβάστε περισσότερα

Kishore Natte, Jianbin Chen, Helfried Neumann, Matthias Beller, and Xiao-Feng Wu*

Kishore Natte, Jianbin Chen, Helfried Neumann, Matthias Beller, and Xiao-Feng Wu* Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 204 Kishore Natte, Jianbin Chen, Helfried Neumann, Matthias Beller, and Xiao-Feng

Διαβάστε περισσότερα

Experimental procedure

Experimental procedure Supporting Information for Direct electrophilic N-trifluoromethylthiolation of amines with trifluoromethanesulfenamide Sébastien Alazet 1,2, Kevin Ollivier 1 and Thierry Billard* 1,2 Address: 1 Institute

Διαβάστε περισσότερα

Copper-Catalyzed Oxidative Coupling of Acids with Alkanes Involving Dehydrogenation: Facile Access to Allylic Esters and Alkylalkenes

Copper-Catalyzed Oxidative Coupling of Acids with Alkanes Involving Dehydrogenation: Facile Access to Allylic Esters and Alkylalkenes Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Supplementary information Copper-Catalyzed xidative Coupling of Acids with Alkanes Involving Dehydrogenation:

Διαβάστε περισσότερα

Synthesis and evaluation of novel aza-caged Garcinia xanthones

Synthesis and evaluation of novel aza-caged Garcinia xanthones Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry Synthesis and evaluation of novel aza-caged Garcinia xanthones Xiaojin Zhang, a,1 Xiang Li, a,1 Haopeng Sun, * b Zhengyu Jiang,

Διαβάστε περισσότερα

Lewis Acid Catalyzed Propargylation of Arenes with O-Propargyl Trichloroacetimidate: Synthesis of 1,3-Diarylpropynes

Lewis Acid Catalyzed Propargylation of Arenes with O-Propargyl Trichloroacetimidate: Synthesis of 1,3-Diarylpropynes Supporting Information for Lewis Acid Catalyzed Propargylation of Arenes with O-Propargyl Trichloroacetimidate: Synthesis of 1,3-Diarylpropynes Changkun Li and Jianbo Wang* Beijing National Laboratory

Διαβάστε περισσότερα

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2018 Supporting Information Silver or Cerium-Promoted Free Radical Cascade Difunctionalization

Διαβάστε περισσότερα

Oxyhalogenation of thiols and disulfides into sulfonyl chlorides/ bromides in water using oxone-kx(x= Cl or Br)

Oxyhalogenation of thiols and disulfides into sulfonyl chlorides/ bromides in water using oxone-kx(x= Cl or Br) Electronic Supplementary Material (ESI) for Green Chemistry. This journal is The Royal Society of Chemistry 2014 Oxyhalogenation of thiols and disulfides into sulfonyl chlorides/ bromides in water using

Διαβάστε περισσότερα

Supplementary Figure S1. Single X-ray structure 3a at probability ellipsoids of 20%.

Supplementary Figure S1. Single X-ray structure 3a at probability ellipsoids of 20%. Supplementary Figure S1. Single X-ray structure 3a at probability ellipsoids of 20%. S1 Supplementary Figure S2. Single X-ray structure 5a at probability ellipsoids of 20%. S2 H 15 Ph Ac Ac I AcH Ph Ac

Διαβάστε περισσότερα

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2015 Synthesis of 3-omosubstituted Pyrroles via Palladium- Catalyzed Intermolecular Oxidative Cyclization

Διαβάστε περισσότερα

Diastereoselective Access to Trans-2-Substituted Cyclopentylamines

Diastereoselective Access to Trans-2-Substituted Cyclopentylamines Supporting Information Diastereoselective Access to Trans-2-Substituted Cyclopentylamines Antoine Joosten, Emilie Lambert, Jean-Luc Vasse, Jan Szymoniak jean-luc.vasse@univ-reims.fr jan.szymoniak@univ-reims.fr

Διαβάστε περισσότερα

ESI for. A simple and efficient protocol for the palladium-catalyzed. ligand-free Suzuki reaction at room temperature in aqueous DMF.

ESI for. A simple and efficient protocol for the palladium-catalyzed. ligand-free Suzuki reaction at room temperature in aqueous DMF. ESI for A simple and efficient protocol for the palladium-catalyzed ligand-free Suzuki reaction at room temperature in aqueous DMF Chun Liu,* Qijian i, Fanying Bao and Jieshan Qiu State Key Laboratory

Διαβάστε περισσότερα

Copper-Catalyzed Direct Acyloxylation of C(sp 2 ) H Bonds. in Aromatic Amides

Copper-Catalyzed Direct Acyloxylation of C(sp 2 ) H Bonds. in Aromatic Amides Supporting Information for Copper-Catalyzed Direct Acyloxylation of C(sp 2 ) H Bonds in Aromatic Amides Feifan Wang, Qiyan Hu, Chao Shu, Zhiyang Lin, Dewen Min, Tianchao Shi and Wu Zhang* Key Laboratory

Διαβάστε περισσότερα

Supporting Information for Fe-Catalyzed Reductive Coupling of Unactivated Alkenes with. β-nitroalkenes. Contents. 1. General Information S2

Supporting Information for Fe-Catalyzed Reductive Coupling of Unactivated Alkenes with. β-nitroalkenes. Contents. 1. General Information S2 Supporting Information for Fe-Catalyzed Reductive Coupling of Unactivated Alkenes with β-nitroalkenes Jing Zheng, Dahai Wang, and Sunliang Cui* College of Pharmaceutical Sciences, Zhejiang University,

Διαβάστε περισσότερα

Supporting Information

Supporting Information S1 Supporting Information Synthesis of 2-Arylated Hydroxytyrosol Derivatives via Suzuki-Myaura Cross-Coupling Roberta Bernini, a Sandro Cacchi, b* Giancarlo Fabrizi, b* Eleonora Filisti b a Dipartimento

Διαβάστε περισσότερα

SUPPORTING INFORMATION. 1. General... S1. 2. General procedure for the synthesis of compounds 3 and 4 in the absence of AgOAc...

SUPPORTING INFORMATION. 1. General... S1. 2. General procedure for the synthesis of compounds 3 and 4 in the absence of AgOAc... SUPPORTING INFORMATION Table of contents 1. General.... S1 2. General procedure for the synthesis of compounds 3 and 4 in the absence of AgOAc... S2 3. General procedure for the synthesis of compounds

Διαβάστε περισσότερα

Supporting Information. Consecutive hydrazino-ugi-azide reactions: synthesis of acylhydrazines bearing 1,5- disubstituted tetrazoles

Supporting Information. Consecutive hydrazino-ugi-azide reactions: synthesis of acylhydrazines bearing 1,5- disubstituted tetrazoles Supporting Information for Consecutive hydrazino-ugi-azide reactions: synthesis of acylhydrazines bearing 1,5- disubstituted tetrazoles Angélica de Fátima S. Barreto*, Veronica Alves dos Santos, and Carlos

Διαβάστε περισσότερα

Supplement: Intramolecular N to N acyl migration in conformationally mobile 1 -acyl-1- systems promoted by debenzylation conditions (HCOONH 4

Supplement: Intramolecular N to N acyl migration in conformationally mobile 1 -acyl-1- systems promoted by debenzylation conditions (HCOONH 4 Cent. Eur. J. Chem. 9(5) 2011 S164-S175 DI: 10.2478/s11532-011-0082-y Central European Journal of Chemistry Supplement: Intramolecular to acyl migration in conformationally mobile 1 -acyl-1- benzyl-3,4

Διαβάστε περισσότερα

Supporting Information. for. Angew. Chem. Int. Ed. Z Wiley-VCH 2003

Supporting Information. for. Angew. Chem. Int. Ed. Z Wiley-VCH 2003 Supporting Information for Angew. Chem. Int. Ed. Z51171 Wiley-VCH 2003 69451 Weinheim, Germany 1 Tin-Free Radical Allylation of B- Alkylcatecholboranes Arnaud-Pierre Schaffner and Philippe Renaud* University

Διαβάστε περισσότερα

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2017 Supporting Information 1. General experimental methods (S2). 2. Table 1: Initial studies (S2-S4).

Διαβάστε περισσότερα

Novel and Selective Palladium-Catalyzed Annulation of 2-Alkynylphenols to Form 2-Substituted 3-Halobenzo[b]furans. Supporting Information

Novel and Selective Palladium-Catalyzed Annulation of 2-Alkynylphenols to Form 2-Substituted 3-Halobenzo[b]furans. Supporting Information Novel and Selective Palladium-Catalyzed Annulation of 2-Alkynylphenols to Form 2-Substituted 3-Halobenzo[b]furans Liang Yun, Shi Tang, Xu-Dong Zhang, Li-Qiu Mao, Ye-Xiang Xie and Jin-Heng Li* Key Laboratory

Διαβάστε περισσότερα

Peptidomimetics as Protein Arginine Deiminase 4 (PAD4) Inhibitors

Peptidomimetics as Protein Arginine Deiminase 4 (PAD4) Inhibitors Peptidomimetics as Protein Arginine Deiminase 4 (PAD4) Inhibitors Andrea Trabocchi a, icolino Pala b, Ilga Krimmelbein c, Gloria Menchi a, Antonio Guarna a, Mario Sechi b, Tobias Dreker c, Andrea Scozzafava

Διαβάστε περισσότερα

Phosphorus Oxychloride as an Efficient Coupling Reagent for the Synthesis of Ester, Amide and Peptide under Mild Conditions

Phosphorus Oxychloride as an Efficient Coupling Reagent for the Synthesis of Ester, Amide and Peptide under Mild Conditions Supplementary Information for Phosphorus xychloride as an Efficient Coupling Reagent for the Synthesis of Ester, Amide and Peptide under Mild Conditions u Chen,* a,b Xunfu Xu, a Liu Liu, a Guo Tang,* a

Διαβάστε περισσότερα

Ferric(III) Chloride Catalyzed Halogenation Reaction of Alcohols and Carboxylic Acids using - Dichlorodiphenylmethane

Ferric(III) Chloride Catalyzed Halogenation Reaction of Alcohols and Carboxylic Acids using - Dichlorodiphenylmethane Supporting Information Ferric(III) Chloride Catalyzed Halogenation Reaction of Alcohols and Carboxylic Acids using - Dichlorodiphenylmethane Chang-Hee Lee,, Soo-Min Lee,, Byul-Hana Min, Dong-Su Kim, Chul-Ho

Διαβάστε περισσότερα

Copper-promoted hydration and annulation of 2-fluorophenylacetylene derivatives: from alkynes to benzo[b]furans and benzo[b]thiophenes

Copper-promoted hydration and annulation of 2-fluorophenylacetylene derivatives: from alkynes to benzo[b]furans and benzo[b]thiophenes Supporting Information for Copper-promoted hydration and annulation of 2-fluorophenylacetylene derivatives: from alkynes to benzo[b]furans and benzo[b]thiophenes Yibiao Li* 1, Liang Cheng 1, Xiaohang Liu

Διαβάστε περισσότερα

Supporting Information for. Synthesis of ethoxy dibenzooxaphosphorin oxides through

Supporting Information for. Synthesis of ethoxy dibenzooxaphosphorin oxides through Supporting Information for Synthesis of ethoxy dibenzooxaphosphorin oxides through Palladium-catalyzed C(sp 2 ) H activation/c O formation Seohyun Shin, Dongjin Kang, Woo Hyung Jeon and Phil Ho Lee* Address:

Διαβάστε περισσότερα

Supporting Information. Microwave-assisted construction of triazole-linked amino acid - glucoside conjugates as novel PTP1B inhibitors

Supporting Information. Microwave-assisted construction of triazole-linked amino acid - glucoside conjugates as novel PTP1B inhibitors Supporting Information Microwave-assisted construction of triazole-linked amino acid - glucoside conjugates as novel PTP1B inhibitors Xiao-Peng He, abd Cui Li, d Xiao-Ping Jin, b Zhuo Song, b Hai-Lin Zhang,

Διαβάστε περισσότερα

Supplementary Information for

Supplementary Information for Supplementary Information for Organocatalytic Asymmetric Intramolecular [3+2] Cycloaddition: A Straightforward Approach to Access Multiply Substituted Hexahydrochromeno[4,3-b]pyrrolidine Derivatives in

Διαβάστε περισσότερα

Supporting Information

Supporting Information Supporting Information Selective Synthesis of xygen-containing Heterocycles via Tandem Reactions of 1,2-Allenic Ketones with Ethyl 4-Chloroacetoacetate Qiang Wang, a, b Zhouqing Xu b and Xuesen Fan a *

Διαβάστε περισσότερα

Electronic Supplementary Information

Electronic Supplementary Information Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Phosphoric and Phosphoramidic Acids as Bifunctional atalysts for the Ring-pening Polymerization

Διαβάστε περισσότερα

9-amino-(9-deoxy)cinchona alkaloids-derived novel chiral phase-transfer catalysts

9-amino-(9-deoxy)cinchona alkaloids-derived novel chiral phase-transfer catalysts Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2014 9-amino-(9-deoxy)cinchona alkaloids-derived novel chiral phase-transfer

Διαβάστε περισσότερα

Supporting Information

Supporting Information Supporting Information Enantiospecific Synthesis of the Cubitane Skeleton Elisabeth Schöttner, M. Wiechoczek, Peter G. Jones, and Thomas Lindel * TU Braunschweig, Institutes of rganic, Inorganic and Analytical

Διαβάστε περισσότερα

Supporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2006

Supporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2006 Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2006 Silver-Catalyzed Asymmetric Synthesis of 2,3-Dihydrobenzofurans: A New Chiral Synthesis of Pterocarpans Leticia Jiménez-González, Sergio

Διαβάστε περισσότερα

Supporting Information for Synthesis of Fused N-Heterocycles via Tandem C-H Activation

Supporting Information for Synthesis of Fused N-Heterocycles via Tandem C-H Activation This journal is The Royal Society of Chemistry 212 Supporting Information for Synthesis of Fused -Heterocycles via Tandem C-H Activation Ge Meng, Hong-Ying iu, Gui-Rong Qu, John S. Fossey, Jian-Ping Li,*

Διαβάστε περισσότερα

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2017 Modular Synthesis of Propargylamine Modified Cyclodextrins by a Gold(III)-catalyzed Three Component

Διαβάστε περισσότερα

Supporting Information For

Supporting Information For Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2017 Supporting Information For ne-pot synthesis of 2,3-difunctionalized indoles

Διαβάστε περισσότερα

Aluminium-mediated Aromatic C F Bond Activation: Regioswitchable Construction of Benzene-fused Triphenylene. Frameworks

Aluminium-mediated Aromatic C F Bond Activation: Regioswitchable Construction of Benzene-fused Triphenylene. Frameworks Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2016 Aluminium-mediated Aromatic C Bond Activation: Regioswitchable Construction of Benzene-fused Triphenylene

Διαβάστε περισσότερα

Supporting information

Supporting information Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2015 Supporting information TFA-promoted Direct C H Sulfenylation at the C2 position of non-protected

Διαβάστε περισσότερα

Iodine-catalyzed synthesis of sulfur-bridged enaminones and chromones via double C(sp 2 )-H thiolation

Iodine-catalyzed synthesis of sulfur-bridged enaminones and chromones via double C(sp 2 )-H thiolation Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2017 Iodine-catalyzed synthesis of sulfur-bridged enaminones and chromones via

Διαβάστε περισσότερα

Rhodium-Catalyzed Oxidative Decarbonylative Heck-type Coupling of Aromatic Aldehydes with Terminal Alkenes

Rhodium-Catalyzed Oxidative Decarbonylative Heck-type Coupling of Aromatic Aldehydes with Terminal Alkenes Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2015 Electronic Supplementary Information Rhodium-Catalyzed Oxidative Decarbonylative Heck-type

Διαβάστε περισσότερα

Supporting Information

Supporting Information Supporting Information Lewis Acid Mediated [2,3]-Sigmatropic Rearrangement of Allylic α-amino Amides. Jan Blid, Peter Brandt, Peter Somfai*, Department of Chemistry, rganic Chemistry, Royal Institute of

Διαβάστε περισσότερα

Electronic Supporting Information. Synthesis and Reactivity of 18 F-Labeled α,α-difluoro-α-aryloxyacetic Acids

Electronic Supporting Information. Synthesis and Reactivity of 18 F-Labeled α,α-difluoro-α-aryloxyacetic Acids Electronic Supporting Information Synthesis and Reactivity of 18 F-Labeled α,α-difluoro-α-aryloxyacetic Acids Tanatorn Khotavivattana,, Samuel Calderwood,, Stefan Verhoog, Lukas Pfeifer, Sean Preshlock,

Διαβάστε περισσότερα

Catalyst-free transformation of levulinic acid into pyrrolidinones with formic acid

Catalyst-free transformation of levulinic acid into pyrrolidinones with formic acid Catalyst-free transformation of levulinic acid into pyrrolidinones with formic acid Yawen Wei, a Chao Wang,* a Xue Jiang, a Dong Xue, a Zhao-Tie Liu, a and Jianliang Xiao* a,b a Key Laboratory of Applied

Διαβάστε περισσότερα

Supporting information

Supporting information Supporting information Synthesis of Aryl Sulfides: Metal-Free C H Sulfenylation of Electron-Rich Arenes Thomas Hostier, a Vincent Ferey, b Gino Ricci, c Domingo Gomez Pardo a and Janine Cossy*, a a Laboratoire

Διαβάστε περισσότερα

Fischer Indole Synthesis in Low Melting Mixtures

Fischer Indole Synthesis in Low Melting Mixtures Fischer Indole Synthesis in Low Melting Mixtures Sangram Gore, a,b Sundarababu Baskaran* a and Burkhard König* b Supporting Information Table of Contents: General Information General Procedure for the

Διαβάστε περισσότερα

Supporting Information

Supporting Information Supporting Information Gold-catalyzed Cycloisomerization of 1,6-Diyne-4-en-3-ols to form Naphthyl Ketone Derivatives. Jian-Jou Lian and Rai-Shung Liu* Department of Chemistry, National Tsing-Hua University,

Διαβάστε περισσότερα

gem-dichloroalkenes for the Construction of 3-Arylchromones

gem-dichloroalkenes for the Construction of 3-Arylchromones Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2015 Pd(OAc)2/S=PPh3 Accelerated Activation of gem-dichloroalkenes for the Construction of 3-Arylchromones

Διαβάστε περισσότερα

Sequential catalysis for the production of sterically hindered amines: Ruthenium(II)-catalyzed C-H bond activation and hydrosilylation of imines

Sequential catalysis for the production of sterically hindered amines: Ruthenium(II)-catalyzed C-H bond activation and hydrosilylation of imines Electronic Supporting Information Sequential catalysis for the production of sterically hindered amines: Ruthenium(II)-catalyzed C- bond activation and hydrosilylation of imines Bin Li, Charles B. Bheeter,

Διαβάστε περισσότερα

Supporting Information

Supporting Information Supporting Information Transition-metal-free Ring Expansion Reactions of Indene-1,3-dione: Synthesis of Functionalized Benzoannulated Seven-Membered Ring Compounds Qiyi Yao, Lingkai Kong, Mengdan Wang,

Διαβάστε περισσότερα