Supporting Information. Radical Instability in Aid of Efficiency. A Powerful Route to Highly Functional MIDA Boronates
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1 S1 Supporting Information Radical Instability in Aid of Efficiency. A Powerful Route to Highly Functional MIDA Boronates Béatrice Quiclet-Sire and Samir Z. Zard* Laboratoire de Synthèse Organique, CNRS UMR 7652 Ecole Polytechnique, Palaiseau Cedex, France zard@poly.polytechnique.fr Contents: Experimental procedures and spectroscopic data S1-S20 Copies of NMR spectra S21-S52
2 S2 General techniques: All reactions were carried out under dry, oxygen free nitrogen. Thin Layer Chromatography (TLC) was performed on alumina plates precoated with silica gel (Merck silica gel, 60 F254), which were visualized by the quenching of UV fluorescence when applicable ( max = 254 nm and/or 366 nm) and/or by staining with anisadehyde in acidic ethanol solution and/or KMnO 4 in basic water followed by heating. Flash chromatography was carried out on Kieselgel 60 (40-63 µm). Petroleum ether refers to the fraction of petroleum boiling between 40 o C and 60 o C. Melting points were recorded by heating on Reichert plates under a microscope and are uncorrected. Nuclear magnetic resonance spectra were recorded at ambient temperature on a Bruker Avance DPX 400 instrument. Proton magnetic resonance spectra ( 1 H NMR) were recorded at 400 MHz and coupling constants (J) are reported to ± 0.5 Hz. The following abbreviations were utilized to describe peak patterns when appropriate: br = broad, s = singlet, d = doublet, t = triplet, q = quartet and m = multiplet. Carbon magnetic resonance spectra ( 13 C NMR) were recorded at 100 MHz. Chemical shifts ( H, C) are quoted in parts per million (ppm) and are referenced to the residual solvent peak (CDCl 3 : H= 7.27 and C= 77.14; DMSO: H= 2.50 and C= 39.52; CD 3 COCD 3, H= 2.05 and C= 29.84). High-resolution mass spectra were recorded by electron impact ionization (EI) on a JMS-GCmateII mass spectrometer. The quoted masses are accurate to ± 5 ppm. General Procedures Radical xanthate addition on the olefin: A solution of xanthate (1.5-3 mmol) and olefin (1 mmol) in 1,2-dichloromethane or acetonitrile (1.5 ml) was refluxed under nitrogen for 10 min. Then dilauroyl peroxide (DLP) was added portion-wise (10 mol%) every hour until total consumption of the starting olefin. After evaporation of the solvent, the residue was purified by silica gel column chromatography affording the addition product or triturated in the appropriate solvent or the precipitate formed during the reaction was filtered off and washed with the appropriate solvent. Compound 9a The radical addition was carried out on the Cyanomethyl Ethylxanthate 1 6a (3 mmol) in the presence of olefin 13 (2 mmol) and needed DLP (15 mol%). After evaporation under a nitrogen flow, the solid was washed with pentane and
3 S3 triturated with diethyl ether to afford the addition product 9a as a beige solid in 87% yield. Mp C. δ H (400 MHz, acetone-d6) (m, 2H, OCH 2 CH 3 ), 4.41 (d, 1H, J=17.3Hz, OCOCHHN), 4.34 (d, 1H, J=17.0Hz, OCOCHHN), 4.23 (d, 1H, J=17.3Hz, OCOCHHN), 4.16 (d, 1H, J=17.0Hz, OCOCHHN), 3.55 (dd, 1H, J=4.5Hz, J=7.9Hz, CHS), 3.24 (s, 3H, NCH 3 ), 2.57 (m, 2H, CH 2 CN), (m, 1H, CHHCHS), (m, 1H, CHHCHS), 1.42 (t, 3H, J=7.1Hz, OCH 2 CH 3 ). δ C (100 MHz, acetone-d6) (CS), 168.1, (2 OCOCH 2 N), (CN), 71.5 (OCH 2 CH 3 ), 64.0, 63.7 (2OCOCH 2 N), 46.9 (NCH 3 ), 29.6 (CH 2 ), 15.6 (CH 2 ), 13.9 (OCH 2 CH 3 ), CHB was not observed. HRMS (EI) calcd for C 12 H 17 N 2 O 5 S 2 B ; found Compound 9b The radical addition was carried out on the methyl phthalimido xanthate 6b 2 (4.5 mmol) in the presence of olefin 13 (3 mmol) in 1,2-dichloroethane (4.5 ml) and needed DLP (25 mol%). The precipitate formed during the reaction was filtered off and washed with diethyl ether to yield the addition product 9b as a white solid in 79% yield. Mp C. δ H (400 MHz, dmso-d6) 7.84 (m, 4H, 4CHAr), (m, 2H, OCH 2 CH 3 ), 4.40 (d, 1H, J=17.3Hz, OCOCHHN), 4.29 (d, 1H, J=17.3Hz, OCOCHHN), 4.13 (d, 1H, J=17.3Hz, OCOCHHN), 4.07 (d, 1H, J=17.3Hz, OCOCHHN), (m, 2H, NCH 2 ), 3.31 (m, 1H, CHS), 2.93 (s, 3H, NCH 3 ), (m, 1H CHHCHS) (m, 1H, CHHCHS), 1.32 (t, 3H, J=7.1Hz, OCH 2 CH 3 ). δ C (100 MHz, dmso-d6) (CS), 168.3, (2CO), (2CO), (2CHAr), (2CqAr), (2CHAr), 70.6 (OCH 2 CH 3 ), 63.0, 62.7 (2OCOCH 2 N), 46.1 (NCH 3 ), 36.2 (CH 2 ), 31.3 (CH 2 ), 13.5 (OCH 2 CH 3 ), CHB not observed. HRMS (EI) calcd for C 19 H 21 O 7 N 2 S 2 B ; found Compound 9c The radical addition was carried out on the known xanthate 3 (0.75 mmol) in the presence of olefin (0.5 mmol) and needed DLP (20 mol%). Chromatography on a silica gel column (pentane, Et 2 O and a gradient of Et 2 O / Acetone 7/3) gave the
4 S4 addition product 9c in 93% yield as about 1:1 mixture of diastereoisomers (calculated on 1 HNMR spectrum). One diastereoisomer can be crystallised from acetone/ diethyl ether. Diastereoisomer 1 Mp C(acetone/diethyl ether). δ H (400 MHz, acetone-d6) 7.60 (d, 1H, J=8.9Hz, NH), (m, 2H, OCHHCH 3, CHCF 3 ), (m, 1H, OCHHCH 3 ), 4.42 (d, 1H, J=17.3Hz, OCOCHHN), 4.33 (d, 1H, J=16.9Hz, OCOCHHN), 4.19 (d, 1H, J=17.3Hz, OCOCHHN), 4.18 (d, 1H, J=16.9Hz, OCOCHHN), 3.53 (dd, 1H, J=2.8Hz, J=12.4Hz, CHS), 3.21 (s, 3H, NCH 3 ), 2.24 (ddd, 1H, J=3.0Hz, J=10.0Hz, J=11.7Hz, CHH), 1.94 (s, 3H, NCOCH 3 ), (m, 1H, CHH), 1.38 (t, 3H, J=7.1Hz, OCH 2 CH 3 ). δ C (100 MHz, acetone-d6) (CS), 170.4, (NHCO), 168.3, (2OCOCH 2 N), (q, J=282Hz, CF 3 ), 71.5 (OCH 2 CH 3 ), 64.1, 63.8 (2OCOCH 2 N), 49.0 (dq, J=30Hz, CHCF 3 ), 46.9 (NCH 3 ), 30.7, 30.6 (CH 2 ), 23.1, 23.0 (COCH 3 ), 13.9 (OCH 2 CH 3 ), CHB not observed. (ν max /cm -1, CDCl 3 ). HRMS (EI) calcd for C 14 H 20 O 6 N 2 F 3 S 2 B ; found Diastereoisomer 2 (contaminated with first diastereoisomer). δ H (400 MHz, acetone-d6) (m, 1H, CHCF 3 ), (m, 2H, OCH 2 CH 3 ), 4.38 (d, 1H, J=17.1Hz, OCOCHHN), 4.34 (d, 1H, J=17.1Hz, OCOCHHN), 4.22 (d, 1H, J=17.1Hz, OCOCHHN), 4.13 (d, 1H, J=17.1Hz, OCOCHHN), 3.48 (dd, 1H, J=4.3Hz, J=9.5Hz, CHS), 3.13 (s, 3H, NCH 3 ), 2.41 (ddd, 1H, J=2.2Hz, J=9.5Hz, J=13.8Hz, CHH), 2.05 (s, 3H, NCOCH 3 ), 1.81 (ddd, 1H, J=4.3Hz, J=11.1Hz, J=14.1Hz, CHH), 1.39 (t, 3H, J=7.1Hz, OCH 2 CH 3 ). δ C (100 MHz, acetone-d6) (CS), (NHCO), 168.1, (2OCOCH 2 N), (q, J=281Hz, CF 3 ), 71.4 (OCH 2 CH 3 ), 64.0, 63.8 (2OCOCH 2 N), 50.5 (q, J=30Hz, CHCF 3 ), 47.0 (NCH 3 ), 33.8 (CH 2 ), 23.1 (COCH 3 ), 14.0 (OCH 2 CH 3 ), CHB not observed. HRMS (EI) calcd for C 14 H 20 O 6 N 2 F 3 S 2 B ; found Compound 9d The radical addition was carried out on the known xanthate 4 (1.5 mmol) in the presence of olefin (1 mmol) and needed DLP (40 mol%). The solvent was evaporated and the residue was triturated with diethyl ether to yield the addition product as a 4:6 mixture of diastereoisomers and as a white solid in 87% yield δ H (400 MHz, CDCl 3 ) 7.83 (m, 2H, CHAr), 7.48 (m, 3H, CHAr), 6.78 (d, 0.4H, J=8.9Hz, NH), 6.55 (d, 0.6H, J=9.6Hz, NH), 5.16 (m, 0.6H, CHCF 3 ), 5.01 (m, 0.4H, CHCF 3 ), (m, 2H, OCH 2 CH 3 ), (m, 2H, OCOCH 2 N), 3.87 (d, 1H, J=16.9Hz, OCOCHHN), 3.79 (d, 1H, J=16.8Hz, OCOCHHN), 3.48 (dd, 0.4H, J=2.9Hz, J=11.2Hz, CHS), 3.34 (dd, 0.6H, J=2.6Hz, J=10.3Hz, CHS), 2.95 (2s, 3H, NCH 3 )
5 S (t, 0.6H, J=11.6Hz, CHH), 2.36 (m, 0.4H, JCHH), 2.16 (m, 0.4H, CHH), 1.98 (m, 0.6H, CHH), 1.37, 1.33 (2t, 3H, J=7.1Hz, OCH 2 CH 3 ). δ C (100 MHz, dmso-d6) 213.1, (CS, PhCO), 168.6, 168.4, 168.3, (2OCOCH 2 N), 167.0, (PhCO), (CqAr), 131.8, (CHAr), 128.3, (CHAr), 127.7, (CHAr), (q, J=283Hz, 0.6CF 3 ), (q, J=283Hz, 0.4CF 3 ), 70.5 (OCH 2 CH 3 ), 63.1, 63.0 (OCOCH 2 N), 62.8, 62.8 (OCOCH 2 N), 50.0 (q, J=29Hz, 0.4CHCF 3 ), 48.2 (q, J=29Hz, 0.6CHCF 3 ), 46.1 (NCH 3 ), 33.5, 33.0 (br, CHB), 31.3, 28.5 (CH 2 ), 13.4, 13.2 (OCH 2 CH 3 ). HRMS (EI) calcd for C 19 H 22 N 2 O 6 S 2 BF ; found Compound 9e The radical addition was carried out on the O-octadecyl S- (trifluoromethyl)carbonodithioate 5 (0.75 mmol) in the presence of olefin (0.5 mmol) and needed DLP (10 mol%). Chromatography on a silica gel column (pentane, Et 2 O and a gradient of Et 2 O / Acetone 7/3) gave the addition product 9e as a white solid in 49% yield and a fraction containing 14% of 9e (NMR estimated) (overall yield 63%). Mp C. δ H (400 MHz, CDCl 3 ) (m, 1H, OCHH), (m, 1H, OCHH), 4.02 (d, 1H, J=16.1Hz, OCOCHH), 3.97 (d, 1H, J=16.9Hz, OCOCHH), 3.94 (d, 1H, J=16.1Hz, OCOCHH), 3.87 (d, 1H, J=16.9Hz, OCOCHH), 3.61 (dd, 1H, J=2.5Hz, J=9.8Hz, CHS), 3.06 (s, 3H, NCH 3 ), (m, 1H, CHH) (m, 1H, CHH), 1.80 (m, 2H), 1.26 (m, 30H, 15CH 2 ), 0.88 (t, 3H, J=6.8Hz, CH 2 CH 3 ). δ C (100 MHz, CDCl 3 ) (CS), 166.9, (2OCOCH 2 N), (q, J=279Hz, CF 3 ), 75.6 (OCH 2 ), 63.8, 63.2 (2OCOCH 2 N), 46.2 (NCH 3 ), 35.8 (q, J=28.3Hz, CH 2 CF 3 ), 32.0, 29.8, 29.7, 29.6, 29.5, 29.3, 28.2, 25.9, 22.8 (16CH 2 ), 14.2 (CH 3 ), CHB not observed. HRMS (EI) calcd for C 27 H 47 O 5 NS 2 BF ; found Compound 9f The radical addition was carried out on the S-chlorodifluoromethyl O- octadecyloxy carbonodithioate 6 (1.5 mmol) in the presence of olefin (1 mmol) and needed DLP (10 mol%). Chromatography on a silica gel column (elution with pentane, Et 2 O and a gradient of Et 2 O / Acetone 7/3) gave the addition product 9f as a white solid in 80% yield. Mp C. δ H (100 MHz, acetone-d6) 4.67 (m, 1H,
6 S6 OCHHCH 2 ), 4.58 (m, 1H, OCHHCH 2 ), 4.45 (d, 1H, J=17.3Hz, OCOCHHN), 4.37 (d, 1H, J=17.0Hz, OCOCHHN), 4.24 (d, 1H, J=17.2Hz, OCOCHHN), 4.21 (d, 1H, J=17.0Hz, OCOCHHN), 3.81 (dd, 1H, J=1.4Hz, J=10.1Hz, CHS), 3.30 (s, 3H, NCH 3 ), 3.00 (m, 1H, CHHCF 2 Cl), 2.76 (m, 1H, CHHCF 2 Cl), 1.84 (m, 2H, CH 2 ), 1.43 (m, 2H, CH 2 ), 1.29 (bs, 28H, 14CH 2 ), 0.88 (t, 3H, J=6.8Hz, CH 2 CH 3 ). δ C (100 MHz, acetoned6) (CS), 167.9, (2OCO), (t, J=294Hz, CqF 2 ), 75.4 (OCH 2 CH 2 ), 64.5, 64.1 (2OCOCH 2 N), 46.9 (NCH 3 ), 44.5 (t, J=23Hz, CH 2 CF 2 Cl), 32.6, 30.4, 30.3, 30.2, 30.1, 29.9, 28.8, 26.5, 23.3 (16CH 2 ), 14.4 (CH 2 CH 3 ), CHB was not observed. HRMS (EI) calcd for C 27 H 47 NO 5 S 2 ClF 2 B ; found Compound 9g The radical addition was carried out on the O-ethyl-S-(4- chlorophenylthio)difluoromethyl xanthate 7 (0.98 mmol) in the presence of olefin (0.65 mmol) and needed DLP (10 mol%).the solvent was evaporated and the residue was triturated with diethyl ether to yield the addition product 9g as a light beige solid in 86% yield. Mp C. δ H (400 MHz, acetone-d6) 7.64 (d, 2H, J=8.5Hz, 2CHAr), 7.50 (d, 2H, J=8.6Hz, 2CHAr), (m, 2H, OCH 2 CH 3 ), 4.44 (d, 1H, J=17.3Hz, OCOCHHN), 4.35 (d, 1H, J=17.3Hz, OCOCHHN), 4.24 (d, 1H, J=16.8Hz, OCOCHHN), 4.19 (d, 1H, J=16.8Hz, OCOCHHN), 3.82 (dd, 1H, J=1.1Hz, J=9.9Hz, CHS), 3.29 (s, 3H, NCH 3 ), 2.78 (m, 1H, CHHCHS), 2.47 (m, 1H, CHHCHS), 1.41 (t, 3H, J=7.1Hz, OCH 2 CH 3 ). δ C (100 MHz, acetone-d6) (CS), 168.0, (2 OCOCH 2 N), (2CHAr), (CqAr), (t, J=281Hz, CF 2 ), (2CHAr), (t, J=2.4Hz CqAr), 71.3 (OCH 2 CH 3 ), 64.5, 64.1 (2OCOCH 2 N), 47.0 (NCH 3 ), 41.4 (t, J=23Hz, CH 2 CF 2 ), 13.9 (OCH 2 CH 3 ), CHB was not observed. HRMS (EI) calcd for C 17 H 19 NO 5 S 3 ClBF ; found Compound 9h The radical addition was carried out on the known xanthate 8 (3 mmol) in the presence of olefin (2 mmol) and needed DLP (10 mol%). Chromatography on a silica gel column (pentane, Et 2 O and a gradient of Et 2 O / Acetone 7/3) gave the addition product 9h as a yellow oil in 93% yield. δ H (400 MHz, CDCl 3 ) (m, 2H, OCH 2 CH 3 ), (m, 6H, 2CO 2 CH 2 CH 3, OCOCH 2 N), 3.96 (tapp, 2H, J=17.2Hz,
7 S7 OCOCH 2 N), 3.60 (dd, 1H, J=3.7Hz, J=10.3Hz, CH), 3.38 (dd, 1H, J=3.3Hz, J=11.2Hz, CH), 3.05 (s, 3H, NCH 3 ), 2.64 (m, 1H, CHH), 2.02 (m, 1H, CHH), 1.40 (t, 3H, J=7.0Hz, OCH 2 CH 3 ), 1.24 (t, 3H, J=7.1Hz, CO 2 CH 2 CH 3 ), 1.23 (t, 3H, J=7.1Hz, CO 2 CH 2 CH 3 ). δ C (100 MHz, CDCl 3 ) (CS), 169.7, 169.3, 167.8, (2CO 2 CH 2 CH 3 and 2OCOCH 2 N), 71.2 (OCH 2 CH 3 ), 63.4, 63.1 (2CO 2 CH 2 CH 3 ), 61.7, 61.6 (2OCOCH 2 N), 49.6 (CH), 46.3 (NCH 3 ), 36.4 (br, CHB), 31.1 (CH 2 ), 14.1, 13.8 (2CO 2 CH 2 CH 3, OCH 2 CH 3 ). HRMS (EI) calcd for C 17 H 26 O 9 NS 2 B ; found Compound 9i The radical addition was carried out on the O-ethyl-S-(1- methoxycarbony)ethyldithiocarbonate 9 (0.82 mmol) in the presence of olefin (0.54 mmol) and needed DLP (20 mol%). The solvent was evaporated and the residue was triturated and washed with diethyl ether to afford the addition product 9i as a 6:4 mixture of diastereoisomers and as a white solid in 94% yield. δ H (400 MHz, acetone-d6) (m, 2H, OCH 2 CH 3 ), 4.39, 4.37, 4.32, 4.31 (4d, J = 17.2, 17.3, 16.9, 17.0 Hz, 2H, OCOCH 2 N), 4.19, 4.18, 4.15, 4.13 (4d, J = 17.0, 17.3, 16.9, 17.0 Hz, 2H, OCOCH 2 N), 3.62 (s, 3H, CO 2 CH 3 ), 3.51 (dd, J = 10.3, 4.7 Hz, 0.4H, CHS), 3.43 (dd, J = 11.0, 3.9 Hz, 0.6H, CHS), (2s, 3H, NCH 3 ), 2.72 (m, 0.6H, CH), 2.43 (m, 0.4H, CH), 2.39 (m, 0.6H, CHHCHS), 1.98 (m, 0.8H, CHHCHS), 1.52 (m, 0.6H, CHHCHS), 1.41, 1.39 (2t, J = 7.2 Hz, J = 7.1 Hz, 3H, OCH 2 CH 3 ), 1.19 (d, J = 6.9 Hz, 1.2H, CH 3 CH), 1.19 (d, J = 7.1 Hz, 1.8H, CH 3 CH). δ C (100 MHz, acetone-d6) 215.8, (CS), 177.0, (CO 2 CH 3 ), 168.4, 168.3, (2OCOCH 2 N), 71.4, 71.2 (OCH 2 CH 3 ), 64.1, 63.9 (2 OCOCH 2 N), 51.8, 51.7 (CO 2 CH 3 ), 46.8, 46.7 (NCH 3 ), 37.9, 37.8, 37.1, 36.2 (CH, CH 2 ), 18.9, 17.4 (CH 3 ), 13.9 (OCH 2 CH 3 ). CHB was not observed. HRMS (EI) calcd for C 14 H 22 O 7 NBS ; found Compound 9j (B-2144) The radical addition was carried out on the known xanthate 10 (3 mmol) in the presence of olefin (2 mmol) and needed DLP (20 mol%). Chromatography on a silica gel column (pentane, Et 2 O and a gradient of Et 2 O / Acetone 7/3) gave the addition
8 S8 product 9j as a white solid in 87% yield. Mp C. δ H (400 MHz, CDCl 3 ) 7.68 (d, 1H, J=8.9Hz, CHAr), 6.44 (dd, 1H, J=2.5Hz, J=8.9Hz, CHAr),6.40 (d, 1H, J=2.5Hz, CHAr), (m, 1H, OCHHCH 3 ), (m, 1H, OCHHCH 3 ), 3.97 (s, 2H, OCOCH 2 ), 3.97 (d, 1H, J=16.9Hz, OCOCHH), 3.89 (d, 1H, J=16.9Hz, OCOCHH), 3.83 (s, 3H, OCH 3 ), 3.52 (dd, 1H, J=4.1Hz, J=8.1Hz, CHS), 3.12 (m, 2H, CH 2 CO), 3.05 (s, 3H, NCH 3 ), (m, 1H, CHHCHS), (m, 1H, CHHCHS), 1.39 (t, 3H, J=7.1Hz, OCH 2 CH 3 ). δ C (100 MHz, CDCl 3 ) (CS), (COAr), 167.5, 167.0, 166.0, (2CqAr, 2OCOCH 2 N), (CHAr), (CqAr), (CHAr), (CHAr), 71.1 (OCH 2 CH 3 ), 63.4, 63.1 (2OCOCH 2 N), 55.6 (OCH 3 ), 46.3 (NCH 3 ), 37.4 (weak, CHB), 35.5 (CH 2 CO), 26.7 (CH 2 CHS), 13.8 (OCH 2 CH 3 ). HRMS (EI) calcd for C 19 H 24 O 8 NS 2 B ; found Compound 15 The radical addition was carried out on xanthate 9j (1.55 mmol) in 1,2- dichloroethane and DLP (20 mol%) was added every hour. The reaction needed 140% DLP to go to completion. Lauric acid formed during the reaction was precipitated from acetonitrile and filtered off. After evaporation of the solvent, the solid was washed with pentane to give 48% of reduction product 15 as a white solid. Chromatography of the mother liquor on a silica gel column (pentane, Et 2 O and a gradient of Et 2 O / Acetone 7/3) gave the 16% more of 15 (overall 64% yield). Mp C. δ H (400 MHz, dmso-d6) 12.8 (s, 1H, OH), 7.86 (d, 1H, J=9.0Hz, CHAr), 6.53 (dd, 1H, J=2.5Hz, J=8.9Hz, CHAr), 6.47 (d, 1H, J=2.5Hz, CHAr), 4.17 (d, 2H, J=17.0Hz, OCOCH 2 N), 3.98 (d, 2H, J=17.0Hz, OCOCH 2 N), 3.82 (s, 3H, OCH 3 ), 2.98 (t, 2H, J=7.2Hz, CH 2 ), 2.82 (s, 3H, NCH 3 ), 1.63 (m, 2H, CH 2 ), 0.59 (m, 2H, CH 2 ). δ C (100 MHz, dmso-d6) (ArCO), (2OCOCH 2 N), (CqAr), (CqAr), (CHAr), (CqAr), (CHAr), (CHAr), 61.7 (2OCOCH 2 N), 55.7 (OCH 3 ), 45.6 (NCH 3 ), 40.5 (CH 2 ), 19.6 (CH 2 ), CH 2 B not observed. HRMS (EI) calcd for C 16 H 20 O 7 NB ; found Compound 9k
9 S9 The radical addition was carried out on the known xanthate 11 (1.5 mmol) in the presence of olefin (1 mmol) and needed DLP (40 mol%). Chromatography on a silica gel column (pentane, Et 2 O and a gradient of Et 2 O / Acetone 7/3) gave the addition product 9k as a light beige solid in 64% yield. Mp C. δ H (400 MHz, CDCl 3 ) 7.73 (dd, 1H, J=1.1Hz, J=3.8Hz, CHAr), 7.62 (dd, 1H, J=1.1Hz, J=4.9Hz, CHAr), 7.12 (dd, 1H, J=3.8Hz, J=4.9Hz, CHAr), (m, 1H, OCHHCH 3 ), (m, 1H, OCHHCH 3 ), 3.97 (d, 1H, J=16.8Hz, OCOCHH), 3.97 (s, 2H, OCOCH 2 ), 3.91 (d, 1H, J=16.8Hz, OCOCHH), 3.51 (dd, 1H, J=4.1Hz, J=8.4Hz, CHS), (m, 2H, COCH 2 ), 3.07(s, 3H, NCH 3 ), (m, 1H, CHHCHS), (m, 1H, CHHCHS), 1.39 (t, 3H, J=7.1Hz, OCH 2 CH 3 ). δ C (100 MHz, acetone-d6) (CS), (ArCO), 168.3, (2OCOCH 2 N), (CqAr), 134.4, 132.9, (3CHAr), 71.3 (OCH 2 CH 3 ), 63.9, 63.8 (2OCOCH 2 N), 46.8 (NCH 3 ), 37.5 (CH 2 CO), 27.6 (CH 2 CHS), 13.9 (OCH 2 CH 3 ), CHB not observed. HRMS (EI) calcd for C 16 H 20 O 6 NS 3 B ; found Compound 9l The radical addition was carried out on the known xanthate 12 (0.82 mmol) in the presence of olefin (0.54 mmol) and needed DLP (10 mol%). The solvent was evaporated and the residue was triturated with diethyl ether to yield the addition product 9l as a white solid in 96% yield. Mp C (acetone/diethyl ether). δ H (400 MHz, acetone-d6) 4.64 (m, 2H, OCH 2 CH 3 ), 4.37 (d, J = 17.2 Hz, 1H, OCOCHHN), 4.31 (d, J = 17.0 Hz, 1H, OCOCHHN), 4.20 (d, J = 17.2 Hz, 1H, OCOCHHN), 4.12 (d, J = 17.0 Hz, 1H, OCOCHHN), 3.50 (dd, J = 8.1, 4.2 Hz, 1H, CHS), 3.21 (s, 3H, NCH 3 ), 2.74 (m, 2H, CH 2 CO), 2.19 (m, 1H, CH), 2.00 (m, 1H, CHHCHS), 1.86 (m, 1H, CHHCHS), 1.40 (t, J = 7.1 Hz, 3H, OCH 2 CH 3 ), 0.84 (m, 4H, 2CH 2 ). δ C (100 MHz, acetone-d6) (CS), (CO), 168.3, (2OCOCH 2 N), 71.3 (OCH 2 CH 3 ), 63.9, 63.7 (2OCOCH 2 N), 46.8 (NCH 3 ), 41.4 (CH 2 CO), 38.0 (br, CHS), 26.8 (CHCO), 20.6 (CH 2 CHS), 13.9 (OCH 2 CH 3 ), 10.4, 10.3 (2CH 2 cycl). HRMS (EI) calcd for C 15 H 22 O 6 NBS ; found Compound 9m
10 S10 The radical addition was carried out on the known xanthate 13 (0.82 mmol) in the presence of olefin (0.54 mmol) and needed DLP (10 mol%). The solvent was evaporated and the residue was triturated and washed with pentane to afford the addition product 9m as a 6:4 mixture ofdiastereoisomers and as a white solid in 95% yield. δ H (400 MHz, acetone-d6) (m, 2H, OCH 2 CH 3 ), (m, 6H, 2CH, 2OCOCH 2 N), 3.64 (s, 3H, CO 2 CH 3 ), 3.31, 3.30, (4s, 6H, 2OCH 3 ), (m, 1H, CH), 3.21, 3.18 (2s, NCH 3 ), 3.08 (m, 0.4H, CH), 2.98 (m, 0.6H, CH), 2.34 (m, 0.6H, CHHCHS), 2.27 (m, 0.4H, CHHCHS), 1.97 (m, 0.4H, CHHCHS), 1.83 (m, 0.6H, CHHCHS), 1.42, 1.39 (2t, 3H, OCH 2 CH 3 ). δ C (100 MHz, acetone-d6) 215.6, (CS), 173.7, (CO 2 CH 3 ), 168.4, 168.3, (2OCOCH 2 N), 105.7, (CHO), 71.3, 71.2 (OCH 2 CH 3 ), 63.9, 63.8, 63.7 (2 OCOCH 2 N), 54.6, 54.4, 53.7 (2OCH 3 ), 52.9, 51.9 (CO 2 CH 3 ), 48.7, 47.3 (CHCO 2 CH 3 ), 46.7 (NCH 3 ), 36.9 (br,chb), 32.2, 29.1 (CH 2 ), 13.9 (OCH 2 CH 3 ). HRMS (EI) calcd for (M-SCSOEt) C 13 H 21 O 8 NB ; found Compound 9n The radical addition was carried out on the known xanthate 14 (0.82 mmol) in the presence of olefin (0.54 mmol) and needed DLP (10 mol%). The solvent was evaporated and the residue was triturated with diethyl ether to yield the addition product 9n as a beige solid in 95% yield. Mp C. δ H (400 MHz, acetone-d6) 4.66 (q, J = 7.1 Hz, 2H, OCH 2 CH 3 ), 4.37 (d, J = 17.3 Hz, 1H, OCOCHHN), 4.31 (d, J = 17.0 Hz, 1H, OCOCHHN), 4.20 (d, J = 17.3 Hz, 1H, OCOCHHN), 4.13 (d, J = 17.0 Hz, 1H, OCOCHHN), 3.59 (s, 2H, CH 2 Br), 3.52 (dd, J = 7.5, 4.6 Hz, 1H, CHS), 3.26, 3.25 (2s, 6H, 2OCH 3 ), 3.23 (s, 3H, NCH 3 ), (m, 1H, CHHCHS), (m, 1H, CHHCHS), 1.41 (t, J = 7.1 Hz, 3H, OCH 2 CH 3 ). δ C (100 MHz, acetone-d6) (CS), (CO), 168.3, (2 OCOCH 2 N), Cq(OCH 3 ), 71.2 (OCH 2 CH 3 ), 63.9, 63.7 (2 OCOCH 2 N), 50.2 (2OCH 3 ), 46.8 (NCH 3 ), 39.4 (CH 2 CO), 37.8 (br, CHB), 30.7 (CH 2 Br), 26.2 (CH 2 ), 13.9 (OCH 2 CH 3 ). HRMS (EI) calcd for C 16 H 25 O 8 NBS 2 Br ; found
11 S11 Compound 9o The radical addition was carried out on the known xanthate 15 (0.82 mmol) in the presence of olefin (0.54 mmol) and needed DLP (20 mol%). The solvent was evaporated and the residue was washed with diethyl ether and recrystallized from acetone/diethyl ether to give the addition product 9o as a white solid in 81% yield. Mp C. δ H (400 MHz, acetone-d6) (m, 2H, OCH 2 CH 3 ), 4.39 (d, J = 17.1 Hz, 1H), 4.32 (d, J = 17.1 Hz, 1H), 4.22 (d, J = 17.2 Hz, 1H), 4.13 (d, J = 17.1 Hz, 1H), 3.72 (m, 1H, NCHH), 3.53 (m, 1H, NCHH), 3.36 (t, J = 7.0 Hz, 1H, CHS), 3.16 (s, 3H, NCH 3 ), 2.70 (s, 4H, COCH 2 CH 2 CO), 2.13 (m, 1H, CHHCHS), 1.80 (m, 1H, CHHCHS), 1.39 (t, J = 7.1 Hz, 3H, OCH 2 CH 3 ). δ C (100 MHz, dmso-d6) (CS), (2CON), 168.4, (2OCOCH 2 N), 70.8 (OCH 2 CH 3 ), 63.1, 62.8 (2OCOCH 2 N), 46.1 (NCH 3 ), 36.7 (NCH 2 ), 34.9 (br, CHB), 30.5 (CH 2 CHS), 28.1 (COCH 2 CH 2 CO), 13.6 (OCH 2 CH 3 ). Mp C (decomp). HRMS (EI) calcd for (M-SCSOEt) C 12 H 16 O 6 N 2 B ; found Compound 9p The radical addition was carried out on the known xanthate 16 (1.5 mmol) in the presence of olefin (1 mmol) and needed DLP (30 mol%).the precipitate formed during the reaction was filtered off and washed with pentane to yield the addition product 9p as a wite solid in 30% yield. 14% of the latter product was isolated from the mother liquor. Mp C. δ H (400 MHz, dmso-d6) 8.05 (d, 1H, J=8.4Hz, CHAr), 7.76 (d, 1H, J=8.4Hz, CHAr), 7.56 (m, 1H, CHAr), 7.41 (m, 1H, CHAr), (2m, 2H, OCH 2 CH 3 ), (m, 2H, NCH 2 ), 4.41 (d, 1H, J=17.3Hz, OCOCHH), 4.32 (d, 1H, J=17.3Hz, OCOCHH), 4.16 (d, 1H, J=17.3Hz, OCOCHH), 4.09 (d, 1H, J=17.3Hz, OCOCHH), 3.40 (dd, 1H, J=5.4Hz, J=7.3Hz, CHS), 2.95 (s, 3H, NCH 3 ), (m, 1H, CHHCHS), (m, 1H, CHHCHS), 1.27 (t, 1H, J=7.1Hz, OCH 2 CH 3 ). δ C (100 MHz, dmso-d6) (CS), 168.4, (2OCOCH 2 N), (CqAr), (CqAr), 127.2, 123.9, 119.2, (4CHAr), 70.6 (OCH 2 CH 3 ), 63.0, 62.8 (2OCOCH 2 N), 46.2 (NCH 3 ), 46.0 (CH 2 ), 31.9 (CH 2 ), 13.4 (OCH 2 CH 3 ), CHB not observed. HRMS (EI) calcd for C 17 H 21 O 5 N 4 S 2 B ; found
12 S12 Compound 9q The radical addition was carried out on the known xanthate 17 (1.23 mmol) in the presence of olefin (0.6 mmol) and needed DLP (60 mol%). Chromatography on a silica gel column (pentane, Et 2 O and a gradient of Et 2 O / Acetone 8/2) gave the addition product as a solid in 34% yield (73% conversion yield). Mp C. δ H (400 MHz, acetone-d6) 8.26 (d, J = 2.5 Hz, 1H, CHAr), 7.70 (dd, J = 8.2, 2.6 Hz, 1H, CHAr), 7.35 (d, J = 8.1 Hz, 1H, CHAr), 4.65 (m, 2H, OCH 2 CH 3 ), 4.40 (d, J = 17.2 Hz, 1H, OCOCHHN), 4.32 (d, J = 16.9 Hz, 1H, OCOCHHN), 4.22 (d, J = 17.2 Hz, 1H, OCOCHHN), 4.15 (d, J = 17.0 Hz, 1H, OCOCHHN), 3.55 (dd, J = 7.8, 4.5 Hz, 1H, CHS), 3.21 (s, 3H, NCH 3 ),2.82 (m, 2H, CH 2 ), 2.19 (m, 1H, CHHCHS), 1.97 (m, 1H, CHHCHS), 1.39 (t, J = 7.1 Hz, 3H, OCH 2 CH 3 ). δ C (100 MHz, acetone-d6) (CS), 168.4, (2OCOCH 2 N), (CHAr), (CqAr), (CHAr), (CqAr), (CHAr), 71.3 (OCH 2 CH 3 ), 63.9, 63.7 (2OCOCH 2 N), 46.8 (NCH 3 ), 38.4 (br, CHB), 34.8 (CH 2 ), 30.7 (CH 2 ), 13.9 (OCH 2 CH 3 ), HRMS (EI) calcd for (M-CH 3 ) C 15 H 17 O 5 N 2 BS 2 Cl ; found Compound 9r The radical addition was carried out on the known xanthate 18 (0.51 mmol) in the presence of olefin (0.34 mmol) and needed DLP (30 mol%). The solvent was evaporated and the residue was chromatographed on a silica gel column using a gradient of elution (diethyl ether/acetone : 10/0 to 7/3) to give the addition product as a white solid in 57% yield. Mp C. δ H (400 MHz, acetone-d6) (m, 5H, Ph), (m, 2H, OCH 2 CH 3 ), 4.38 (m, 2H, NCH 2 Ph), 4.36 (d, J = 17.2 Hz, 1H, OCOCHHN), 4.30 (d, J = 17.0 Hz, 1H, OCOCHHN), 4.19 (d, J = 17.2 Hz, 1H, OCOCHHN), 4.11 (d, J = 17.0 Hz, 1H, OCOCHHN), 3.53 (dd, J = 8.3, 4.0 Hz, 1H, CHS), 3.19 (s, 3H, NCH 3 ), 2.41 (m, 2H, CH 2 ), (m, 1H, CHHCHS), (m, 1H, CHHCHS), 1.38 (t, J = 7.1 Hz, 3H, OCH 2 CH 3 ). δ C (100 MHz, acetone-d6) (CS), (Cq), 168.4, (2 OCOCH 2 N), (Cq), 129.1,
13 S , (5CHAr), 71.2 (OCH 2 CH 3 ), 63.9, 63.7 (2OCOCH 2 N), 46.8 (NCH 3 ), 43.4 (CH 2 ), 34.3 (CH 2 ), 28.7 (CH 2 CHS), 13.9 (OCH 2 CH 3 ), CHB was not observed. HRMS not found. Compound 9s The radical addition was carried out on the known xanthate 19 (0.82 mmol) in the presence of olefin (0.54 mmol) and needed DLP (30 mol%). The solvent was evaporated and the residue was chromatographed on a silica gel column using a gradient diethyl ether/acetone (10/0 to 2/8) to give the addition product as a white solid in 83% yield. Mp C. δ H (400 MHz, acetone-d6) (mixture of conformers). δ H (400 MHz, acetone-d6) (m, 2H, CHAr), (m, 2H, CHAr), (td, J = 13.4, 5.2 Hz, 1H, NCHH), (m, 2H, OCH 2 CH 3 ), (m, 3H, NCHH, OCOCH 2 N), 4.16, 4.15 (2d, J = 17.3 Hz, 1H, OCOCHHN), (2d, J = 17.1 Hz, 1H, OCOCHHN), (m, 1H, CONCHH), (m, 1H, CONCHH), 3.34 (dd, J = 12.7, 6.9 Hz, 1H, CHS), 3.15 (s, 3H, NCH 3 ), (m, 1H, CHH), 2.27 (m, 1H, CHH), (m, 1H, CHH), (m+s, 4H, NC0CH 3, CHH), 1.36, 1.34 (2t, J = 7.1 Hz, 3H, OCH 2 CH 3 ). δ C (100 MHz, acetoned6) (mixture of conformers) (CS), 170.9, 170.8, (2CO), 168.4, 168.3, (2 OCOCH 2 N), 141.5, (CqAr), 136.4, (CqAr), 130.6, 130.1, 127.7, (4CHAr), 71.3, 71.2 (OCH 2 CH 3 ), 63.9, 63.6 (2OCOCH 2 N), 48.3, 48.2 (CH 2 ), 46.8 (NCH 3 ), 46.3, 45.5 (CH 2 ), 36.4 (br, CHB), 34.1 (CH 2 ), 31.8, 31.6 (CH 2 ), 22.6, 22.5 (NCOCH 3 ), 13.9 (OCH 2 CH 3 ). HRMS (EI) calcd for C 22 H 28 O 7 N 3 S 2 B ; found Compound 9t The radical addition was carried out on the known xanthate 20 (0.82 mmol) in the presence of olefin (0.54 mmol) and needed DLP (20 mol%). The solvent was evaporated and the residue was triturated with diethyl ether to yield the addition product as a white solid in 92% yield. Mp C. δ H (400 MHz, acetone-d6)
14 S (m, 2H, OCH 2 CH 3 ), 4.43 (d, J = 17.1 Hz, 1H, OCOCHHN), 4.35 (d, J = 17.1 Hz, 1H, OCOCHHN), 4.24 (d, J = 17.2 Hz, 1H, OCOCHHN), 4.17 (d, J = 17.2 Hz, 1H, OCOCHHN), 3.63 (dd, J = 7.5, 4.7 Hz, 1H, CHS), 3.23 (s, 3H, NCH 3 ), 3.18 (t, J = 8.1 Hz, 2H, CH 2 ), (m, 1H, CHHCHS), (m, 1H, CHHCHS), 1.40 (t, J = 7.1 Hz, 3H, OCH 2 CH 3 ). δ C (100 MHz, acetone-d6) (CS), (Cq=N), 168.3, (2 OCOCH 2 N), (q, J= 44Hz, CF 3 Cq), (q, J= 270Hz, CF 3 ), 71.6 (OCH 2 CH 3 ), 64.0, 63.7 (2OCOCH 2 N), 46.9 (NCH 3 ), 38.1 (br, CHB), 29.5 (CH 2 ), 24.1 (CH 2 ), 13.9 (OCH 2 CH 3 ). HRMS (EI) calcd for C 14 H 17 O 6 N 3 F 3 S 2 B ; found Compound 9u The radical addition was carried out on xanthate 21 (0.75 mmol) in the presence of olefin (0.5 mmol) in 1,2-dichloroethane (0.75 ml) and acetonitrile (0.1 ml) and needed DLP (20 mol%). Chromatography on a silica gel column (pentane, Et 2 O and a gradient of Et 2 O / Acetone 7/3) gave a 1:1 mixture of the diastereoisomers of the addition product 9u in 71% yield and as a white solid and contaminated with 6% of the olefin (NMR estimated). δ H (400 MHz, acetone-d6) Selected signals 5.67 (s, 1H, CH=C), (m, 2H, OCH 2 CH 3 ), (m and several d, 5H, CHOH, 2OCOCH 2 N), 3.54 (dd, 0.5H, J=4.3, J=7.9Hz, CHS), 3.47 (dd, 0.5H, J=5.5, J=6.9Hz, CHS), 3.22 (2s, 3H, NCH 3 ), 1.60 (s, 3H, CH 3 ), 1.40 (t, 3H, J=7.1Hz, OCH 2 CH 3 ), 0.87 (s, 3H, CH 3 ). δ C (100 MHz, acetone-d6) 216.1, (CS), 212.2, (CO), (CO), 170.9, 169.7, 169.6, 169.0, 168.8, 168.7, 168.1, (C=CH, 2OCOCH 2 N), 129.4, (CH=C), (d, J= 172Hz, CF), 90.6, 90.5 (C-OH), 71.24, (CH 2 ), 71.17, 70.84, (CH), 64.0, 63.75, 63.73, 62.2, 60.5 (CH 2 ), 47.3, 46.8, 46.7, 46.6, 46.2, 46.19, 46.15, (CH, NCH 3 ), 44.7, 44.6 (Cq), 38.0, 37.2, 37.0, 36.9 (CH 2 ), 35.0, 34.9 (CH, CH 3 ), 34.4, 33.77, 33.71, 31.4, 29.2, 29.1, 27.6, 27.4, 27.1, 24.1, 24.0 (CH 2 ), 22.25, 22.22, 22.19, 22.16, 20.8, 17.4, 17.2, 14.4, 14.0, (CH, CH 3 ). HRMS not found. Compound 9v
15 S15 The radical addition was carried out on the known xanthate 22 (1.3 mmol) in the presence of olefin (1 mmol) in 1,2-dichloroethane (1.5 ml) and needed DLP (25 mol%). Evaporation of the solvent and chromatography of the residue on a silica gel column (pentane, Et 2 O and a gradient of Et 2 O / Acetone 8/2) gave the addition product 9v as about 1:1 mixture of diastereoisomers in 57% yield. First diastereoisomer Isolated as a white solid. Mp C δ H (400 MHz, CDCl 3 ) 4.71 (td, 1H, J=2.7Hz, J=11.4Hz, CHN), 4.60 (m, 2H, OCH 2 CH 3 ), 4.29 (d+m, 2H, J=16.2Hz, OCOCHHN, CH), 3.86 (d, 1H, J=16.1Hz, OCOCHHN), 3.82 (d, 1H, J=16.1Hz, OCOCHHN), 3.81 (d, 1H, J=16.1Hz, OCOCHHN), 3.70 (dd, 1H, J=2.9Hz, J=12.2Hz, CH), 3.07 (s, 3H, NCH 3 ), 2.74 (t, 1H, J=3.5Hz, CH), 2.40 (s, 3H, NCOCH 3 ), (m, 1H, CH), 2.00 (m, 1H, CH), 1.41 (t, 3H, J=7.1Hz, OCH 2 CH 3 ), 1.24 (d, 3H, J=6.2Hz, CH 3 CH), 0.84 (s, 9H, SiMe 3 ), 0.09 (s, 3H, SiCH 3 ), 0.06 (s, 3H, SiCH 3 ). δ C (100 MHz, CDCl 3 ) (CS), 169.6, 167.6, 167.1, (4CO), 70.7 (OCH 2 CH 3 ), 65.2 (CH), 63.9 (CH), 63.3, 63.2 (2OCOCH 2 N), 52.6 (CH), 46.5 (NCH 3 ), 40.9 (CH 2 ), 25.6 (CMe 3 ), 24.3 (CH 3 ), 22.1 (CH 3 ), 17.8 (CMe 3 ), 13.9 (OCH 2 CH 3 ), -4.1, -5.1 (SiMe 2 ), CHB not observed. HRMS (EI) calcd for (M-C 4 H 9 ) C 19 H 30 O 8 N 2 S 2 SiB ; found Second diastereoisomer 9v was isolated as a white solid. Mp C. δ H (400 MHz, CDCl 3 ) (m, 3H, OCH 2 CH 3, CHN), 4.32 (m, 1H, CH), (m, 5H, 2OCOCH 2 N, CH), 3.07 (m, 3H, NCH 3 ), (m, 1H, CHH), (m, 1H, CH), 2.30 (s, 3H, NCOCH 3 ), 2.00 (td, 1H, J=4.8Hz, J=14.8Hz, CH), 1.42 (t, 3H, J=7.1Hz, OCH 2 CH 3 ), 1.23 (d, 3H, J=6.3Hz, CH 3 CH), 0.82 (s, 9H, CMe 3 ), 0.06 (s, 3H, SiCH 3 ), 0.03 (s, 3H, SiCH 3 ). 13 C NMR (101 MHz, CDCl 3 ) (CS), 168.8, 167.2, 167.0, (4CO), 71.0 (OCH 2 CH 3 ), 64.8 (CH), 63.5, 63.2 (2OCOCH 2 N), 63.0 (CH), 52.9 (CH), 46.4 (NCH 3 ), 38.1 (CH 2 ), 25.7 (CH 3 ), 25.6 (CMe 3 ), 24.2 (CH 3 ), 22.2 (CH 3 ), 17.8 (CMe 3 ), 13.9 (OCH 2 CH 3 ), -4.09, (SiMe 2 ), CHB not observed. HRMS (EI) calcd for (M-C 4 H 9 ) C 19 H 30 O 8 N 2 S 2 SiB ; found Compound 9w The radical addition was carried out on the known xanthate 23 (0.75 mmol) in the presence of olefin (0.5 mmol) and needed DLP (20 mol%). Chromatography on a silica gel column using a gradient of elution (pentane, Et 2 O, Et 2 O / Acetone 7/3) gave the addition product as a 1:1 mixture of diastereoisomers and as a white solid in 93% yield. δ H (400 MHz, CDCl 3 ) 5.00 (dd, 0.5H, J=2.9Hz, J=8.1Hz, CH),
16 S16 (m, 2.5H, CH, OCH 2 CH 3 ), 4.48 (t, 0.5H, J=6.8Hz, CH), 4.32 (t, 0.5H, J=4.1Hz, CH), (m, 2.5H, OCOCH 2 N), 3.95, 3.92, 3.90 (3d, 1.5H, J=17.4Hz, J=16.6Hz, J=16.7Hz, OCOCHHN), 3.35 (t, 0.5H, J=7.3Hz, CHS), 3.28 (dd, 0.5H, J=3.3Hz, J=10.9Hz, CHS), 3.10 (s, 1.5H, NCH 3 ), 3.02 (m, 1H, CHHCN), 3.0 (s, 1.5H, NCH 3 ), 2.84 (m, 1H, CHHCN), 2.58, 2.57, 2.55, 2.49 (4s, 6H, 2NCOCH 3 ), 2.48 (m, 0.5H, CHH), 2.21 (m, 0.5H, CHH), 2.04 (m, 0.5H, CHH), 1.81 (m, 0.5H, CHH), 1.43 (t, 1.5H, J=7.1Hz, OCH 2 CH 3 ), 1.42 (t, 1.5H, J=7.1Hz, OCH 2 CH 3 ). δ C (100 MHz, CDCl 3 ) 215.7, (CS), 171.4, (CO), 170.7, (CO), 168.4, (CO), 167.7, (CO), 150.9, (CO), 117.2, (CN), 71.5, 71.4 (OCH 2 CH 3 ), 63.7, 63.4, 63.3 (2CH 2 ), 54.8, 54.7 (CH), 52.7, 51.4 (CH), 46.6, 46.5 (NCH 3 ), 37.7, 35.9 (CH 2 ), 24.6, 24.5, 24.48, (2COCH 3 ), 21.9, 21.7 (CH 2 ), 13.9 (OCH 2 CH 3 ). CHB was not observed. HRMS (EI) calcd for C 19 H 25 N 4 O 8 S 2 B ; found Compound 17 A solution of xanthate 9w (0.43 mmol) in 2-propanol (2 ml) was refluxed under nitrogen for 10 min and DLP (20%) was added every hour until total consumption of the starting xanthate (120% DLP were needed). The reaction mixture was cooled and evaporated. The residue was purified on a silica gel column using a gradient of elution (Et 2 O/Acetone: 10/0 to 6/4). The reduction product 17 was isolated in 60% yield as a white solide. Mp C. δ H (400 MHz, acetone-d6) 4.34 (m, 1H, CH), 4.21 (d, 2H, J=16.9Hz, OCOCH 2 N) 4.17 (m, 1H, CH), 4.05 (d, 1H, J=16.9Hz, OCOCHHN), 4.04 (d, 1H, J=16.9Hz, OCOCHHN), 3.11 (s, 3H, NCH 3 ), 3.06 (dd, 1H, J=6.2Hz, J=17.0Hz, CHHCN), 3.00 (dd, 1H, J=3.9Hz, J=17.0Hz, CHH), 2.48 (s, 3H, COCH 3 ), 2.44 (s, 3H, COCH 3 ), 1.88 (m, 1H, CHH), 1.63 (m, 1H, CHH), 0.78 (td, 1H, J=4.4Hz, J=13.3Hz, CHH), 0.63 (td, 1H, J=4.8Hz, J=13.3Hz, CHH). δ C (100 MHz, dmso-d6) 170.3, (2CO), , (2OCOCH 2 ), , (CO), (CN), 61.8 (2OCOCH 2 N), 57.4 (NCH), 50.9 (NCH), 45.6 (NCH 3 ), 26.8 (CH 2 ), 24.19, (2CH 3 CO), 21.4 (CH 2 CN), 9.8 (br, CH 2 B). HRMS (EI) calcd for C 16 H 21 N 4 O 7 B ; found Compounds 9x and 19
17 S17 The radical addition was carried out on the known xanthate 24 (1.3 mmol) in the presence of olefin (0.9 mmol) and needed DLP (10 mol%). Chromatography on a silica gel column using a gradient of elution (pentane, Et 2 O, Et 2 O / Acetone 7/3) gave the addition product 9x as a white solid in 76% yield and caracterized after reduction of the xanthate group. To a solution of the latter xanthate 9x (0.49 mmol) in acetonitrile (4 ml) were added tris trimethylsilylsilane (0.73 mmol) and AIBN (20 mol%); The reaction mixture was refluxed under nitrogen until total consumption of the starting xanthate and then cooled to room temperature and evaporated. The residue was purified on a silica gel column using a gradient of elution (Et 2 O/Acetone : 10/0 to 6/4). The reduction product 19 was isolated in 60% yield as a white solide. δ H (400 MHz, acetone-d6) 7.89 (m, 4H, 4CHAr), (m, 1H, CHO), 4.68 (dd, J = 6.0 Hz, J = 11.5 Hz, 1H, CHO), 4.24 (d, J = 16.9 Hz, 1H, OCOCHHN), 4.23 (d, 1H, J = 16.9 Hz, OCOCHHN), (m, 4H, OCOCH 2 N, NCH 2 Phth), 3.13 (s, 3H, NCH 3 ), 1.86 (m, 2H, CH 2 ), (m, 1H, CHHB), (m, 1H, CHHB). δ C (100 MHz, acetone-d6) (2CO), (2CO), (CO), (2CHAr), (2 Cq) (2 CHAr), 82.2 (CH), 79.4 (CH), 62.7 (2 OCOCH 2 N), 46.4 (NCH 3 ), 40.4 (NCH 2 ), 29.0 (CH 2 ), 10.7 (br CH 2 B). HRMS (EI) calcd for (M-CO 2 ) C 18 H 19 O 7 N 2 B ; found Compound 20 A solution of xanthate 9k (0.3 mmol) 1,2-dichloroethane (3 ml) was refluxed under nitrogen for 10 min and DLP (25%) was added every hour until total consumption of the starting xanthate (175% DLP were needed). The reaction mixture was cooled and evaporated. The residue was purified on a silica gel column using a gradient of elution (Et 2 O/Acetone : 10/0 to 6/4). The cyclized product 20 was isolated in 33% yield as a light beige solide. Mp C. δ H (400 MHz, acetone-d6) 7.77 (d, 1H, J=5.0Hz, CHAr), 7.22 (d, 1H, J=5.0Hz, CHAr), 4.33 (d, 1H, J=17.1Hz, OCOCHH), 4.30 (d, 1H, J=17.0Hz, OCOCHH), 4.20 (d, 1H, J=17.1Hz, OCOCHH), 4.09 (d, 1H, J=17.0Hz, OCOCHH), 3.30 (s, 3H, NCH 3 ), 2.79 (t, 1H, J=4.9Hz, CHB), 2.72 (ddd, 1H, J=5.0Hz, J=10.6Hz, J=16.7Hz, CHH), 2.43 (ddd, 1H, J=4.8Hz, J=6.4Hz, J=16.9Hz, CHH), (m, 2H, CH 2 ). δ C (100 MHz, acetone-d6) (CO), 168.6, (2OCOCH 2 N), (CqAr), (CqAr), (CHAr), (CHAr), 63.5, 63.3 (2OCOCH 2 N), 46.7 (NCH 3 ), 37.4 (CH 2 CO), 30.6 (CHB), 26.9 (CH 2 ). HRMS (EI) calcd for C 13 H 14 O 5 NSB ; found
18 S18 Compound 21 The radical addition was carried out on xanthate 9a (0.58 mmol) in the presence of ethyl 2-bromo-2methyl propionate (5.8 mmol) in reflux chlorobenzene (9 ml) containing 0.5 ml of acetontrile under nitrogen. Dicumyl peroxide (50 mol%) was added every hour until 200%. Chromatography on a silica gel column using a gradient of elution (pentane, Et 2 O, Et 2 O / Acetone 8/2) gave the bromo derivative 21 as a white solid in 45% yield. Mp C (diethyl ether/acetone). δ H (400 MHz, acetone-d6) 4.43 (d, J = 17.4 Hz, 1H, OCOCHH), 4.32 (d, J = 16.7 Hz, 1H, OCOCHH), 4.19 (d, J = 17.0 Hz, 2H, OCOCH 2 ), 3.70 (dd, J = 11.2, 3.0 Hz, 1H, CHBr), 3.35 (s, 3H, NCH 3 ), 2.76 (m, 1H, NCCHH), 2.68 (dd, J = 17.1, 8.4 Hz, NCCHH), (m, 1H, CHH), (m, 1H, CHH). δ C (100 MHz, acetoned6) 168.3, (2OCOCH 2 N), (CqN), 64.1, 63.9 (2OCOCH 2 N), 46.2 (NCH 3 ), 30.7 (CH 2 CN), 16.8 (CH 2 ), CHB was not observed. HRMS (EI) calcd for C 9 H 12 O 4 NBrB ; found Compound 22 The radical addition was carried out on xanthate 9i (1.73 mmol) in the presence of ethyl 2-bromo-2methyl propionate (36 mmol) in reflux chlorobenzene (9 ml) under nitrogen. Dicumyl peroxide (50 mol%) was added every hour until 150%. Chromatography on a silica gel column using a gradient of elution (pentane, Et 2 O, Et 2 O / Acetone 8/2) gave the bromo derivative 22 as a white solid in 48% yield. Mp C (diethyl ether/acetone). δ H (400 MHz, CDCl 3 ) (m, 6H, 2CO 2 CH 2, OCOCH 2 N), 3.96 (d, 2H, J=17.0Hz, OCOCH 2 N), 3.81 (dd, 1H, J=3.6Hz, J=10.6Hz, CH), 3.46 (dd, 1H, J=2.1Hz, J=12.1Hz, CH), 3.18 (s, 3H, NCH 3 ), 2.63 (m, 1H, CHH), 2.32 (m, 1H, CHH), 1.28, 1.27 (2t, 6H, J=7.1Hz, 2CO 2 CH 2 CH 3 ). δ C (100 MHz, CDCl 3 ) 169.3, (2CO), 167.9, (2CO), 63.6, 63.4 (2OCOCH 2 N), 61.8, 61.7 (2CO 2 CH 2 CH 3 ), 50.7 (CH), 45.5 (NCH 3 ), 41.9 (br, CHB), 32.8 (CH 2 ), 14.1 (OCH 2 CH 3 ). HRMS (EI) calcd for C 14 H 21 O 8 NBrB ; found
19 S19 Compound 23 A solution of bromide 22 (0.34 mmol) in THF (3 ml) was treated with triethylamine (1.02 mmol) under reflux. Chromatography on a silica gel column (pentane, Et 2 O and a gradient of Et 2 O / Acetone 8/2) gave the cyclopropyl derivative 23 as a white solid in 82% yield. Mp C. δ H (400 MHz, CDCl 3 ) (m, 6H, 2 CO 2 CH 2 CH 3, OCOCH 2 N), 3.89 (d, 2H, J=17.1Hz, OCOCH 2 N), 3.19 (s, 3H, NCH 3 ), 1.42 (m, 1H, CHH), 1.35 (m, 1H, CHH), 1.25, 1.22 (2t, 6H, J=7.1Hz, 2 CO 2 CH 2 CH 3 ), 0.91 (dd, 1H, J=10.7Hz, J=8.7Hz). δ C (100 MHz, CDCl 3 ) 171.2, 169.5, 168,5, (4CO), 63.7, 61.9, 61.8 (2OCOCH 2 N, 2 CO 2 CH 2 CH 3 ), 48.0 (NCH 3 ), 33.3 (Cq), 17.2 (CH 2 ), 14.0, 13.9 (2CO 2 CH 2 CH 3 ), CHB was not observed. HRMS (EI) calcd for C 14 H 20 NO 8 B ; found Dinizo, S. E.; Freerksen, R. W.; Pabst, W. E.; Watt, D. S. J. Org. Chem. 1976, 41, Lo, C.-P. J. Org. Chem. 1961, 26, Gagosz, F.; Zard, S. Z. Org. Lett. 2003, 5, Rhodia Chimie Patent: 2006, US2006/ A1. 5 Li, S. G.; Zard, S. Z. Org.Lett. 2013, 15, Salomon, P. ; Zard, S. Z. Org. Lett. 2014, 16, Salomon, P.; Zard, S. Z. Org. Lett. 2014, 16, Panchaud, P.; Ollivier, C.; Renaud, P.; Zigmantas, S. J. Org. Chem. 2004, 69, Taton, D.; Baussard, JF.; Dupayage, L.; Poly, J.; Gnanou, Y.; Ponsinet, V.; Destarac, M.; Mignaud, C.; Pitois, C. Chem. Commun. 2006, Cordero Vargas, A.; Quiclet-Sire, B.; Zard, S. Z.Org. Lett. 2003, 5, Jullien, H.; Quiclet-Sire, B.; Tetart, T.; Zard, S. Z. Org. Lett. 2014, 16, Boivin, J.; Pothier, J.; Zard, S. Z Tetrahedron Lett. 1999, 40, Tate, E.; Zard, S. Z Tetrahedron Lett. 2002, 43, Synthesized in our laboratory by David Clemente. 15 Quiclet-Sire, B.; Zard, S. Z. Org. Lett. 2008, 10, Katritzky, A. R.; Button, M. A. C.; Denisenko, S. N. Heterocycles, 2001,54, Ferjancic, Z.; Quiclet-Sire, B.; Zard, S. Z. Synthesis, 2008, Biadatti, T.; Quiclet-Sire, B.; Saunier, J.-B.; Zard, S. Z. Tetrahedron Lett. 1998, 39, Lebreux, F.; Quiclet-Sire, B.; Zard, S. Z. Org. Lett. 2009, 11, Qin. L.; Zard, S. Z. Org. Lett. 2015, 17, Debien, L.; Quiclet-Sire, B.; Zard, S. Z. Org. Lett. 2012, 14, Quiclet-Sire, B.; Zard,S. Z. Heterocycles 2010, 82, Han, S.; Zard, S. Z. Org. Lett. 2014, 16, Quiclet-Sire, B.; Zard, S. Z. Org. Lett. 2008, 10, 3279.
20 Compound 9a S21
21 Compound 9b S22
22 Compound 9c (diastereoisomer 1) S23
23 Compound 9c (diastereoisomer 2) S24
24 Compound 9d S25
25 Compound 9e S26
26 Compound 9f S27
27 Compound 9g S28
28 Compound 9h S29
29 Compound 9i S30
30 Compound 9j S31
31 Compound 15 S32
32 Compound 9k S33
33 Compound 9l S34
34 Compound 9m S35
35 Compound 9n S36
36 Compound 9o S37
37 Compound 9p S38
38 Compound 9q S39
39 Compound 9r S40
40 Compound 9s S41
41 Compound 9t S42
42 Compound 9u S43
43 Compound 9v (Diastereoisomer 1) S44
44 Compound 9v (Diastereoisomer 2) S45
45 Compound 9w S46
46 Compound 17 S47
47 Compound 19 S48
48 Compound 20 S49
49 Compound 21 S50
50 Compound 22 S51
51 Compound 23 S52
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