Supporting Information
|
|
- Χριστός Καλάρης
- 5 χρόνια πριν
- Προβολές:
Transcript
1 Supporting Information Synthesis of Pyrrole-Fused C,N-Cyclic Azomethine Imines and Pyrazolopyrrolopyrazines: Analysis of Their Aromaticity Using Nucleus-Independent Chemical Shifts Values Merve Sinem Özer, Nurettin Menges,, Selbi Keskin,,ǁ Ertan Şahin, Metin Balci *, Department of Chemistry, Middle East Technical University, Ankara, Turkey Faculty of Pharmacy, Yüzüncü Yil University, Van, Turkey Department of Chemistry, Atatürk University, 25240, Erzurum, Turkey ǁ Department of Chemistry, Giresun University, Giresun, Turkey Table of Content Page 1. Experimental Section S2 2. General Procedure for compound 12a-h S2 3. General Procedure for compound 13a-h S5 4. General Procedure for compound S7 5. NMR Spectra S10 6. Theoretical Calculations S33 7. Methodology S33 8. Theoretical Coordinates for compound 13a,c,d,f, and S33 9. X-Ray structure determination of 13d S References S42 S1
2 Experimental Section General Methods. NMR spectra were recorded on a 400 MHz spectrometer. Infrared (IR) spectra were recorded in the range cm -1 via ATR diamond. Melting points were determined using a melting point apparatus and were uncorrected. Mass spectra were recorded by LC-MS TOF electrospray ionization technique. Column chromatography was performed on silica gel (60-mesh), TLC was carried out on 0.2 mm silica gel 60 F 254 analytical aluminum plates. Evaporation of solvents was performed at reduced pressure, using a rotary vacuum evaporator. General Procedure for compound 12a-h. Pyrrole aldehyde 9 or 10 (1 equiv.) and hydrazide 11a-e (1 equiv) were stirred in 5 ml EtOH at room temperature for 24 h. Evaporation of the solvent gave the corresponding products 12a-h. N'-((1-(Prop-2-yn-1-yl)-1H-pyrrol-2-yl)methylene)formohydrazide (12a): Pyrrole aldehyde 9 (0.50 g, 3.76 mmol) and formohydrazide (0.23 g, 3.76 mmol) were reacted as described above. After evaporation of the solvent the residue was crystallized from CHCl 3 in petroleum ether atmosphere to give the product 12a as brown crystals (0.66 g, 100%, NMR yield), mp C. 1 H NMR (400 MHz, CDCl 3 ) δ 9.75 (bd, J = 8.8 Hz, 1H), 8.71 (d, J = 10.3 Hz, 1H), 7.79 (s, 1H), 7.04 (dd, J = 2.3, 1.8 Hz, 1H), 6.49 (dd, J = 3.8, 1.7 Hz, 1H), 6.21 (dd, J = 3.7, 2.8 Hz, 1H), 5.13 (d, J = 2.5 Hz, 2H), 2.42 (t, J = 2.5 Hz, 1H); 13 C NMR (101 MHz, CDCl 3 ) δ 179.8, 165.2, 139.3, 127.0, 117.8, 109.5, 78.4, 73.9, 38.8; IR (ATR, cm -1 ) 3186, 1676, 1473, 1396, 1362, 1276, 1069, 1021, 776, 710, 650; HRMS for C 9 H 10 N 3 O [M+H] + : Found: (E/Z)-N'-((1-(Prop-2-yn-1-yl)-1H-pyrrol-2-yl)methylene)acetohydrazide (12b). Pyrrole aldehyde 9 (0.53 g, 4.00 mmol) and acetohydrazide (0.30 g, 4.00 mmol) were reacted as described above. After evaporation of the solvent the residue was crystallized from ethanol to give the product 12b as white sponge crystals (0.76 g, 100%, crude yield). According to NMR calculation, E-isomer 74%, Z-isomer is 26%. E-isomer; 1 H NMR (400 MHz, DMSO-d 6 ) δ (s, 1H), 7.89 (s, 1H), 7.05 (dd, J = 2.4, 2.0 Hz, 1H), 6.43 (dd, J = 3.7, 1.7 Hz, 1H), 6.11 (dd, J = 3.6, 2.8 Hz, 1H), 5.10 (d, J = 2.4 Hz, 2H), 3.35 (t, J = 2.4 Hz, 1H), 2.16 (s, 3H); 13 C NMR (101 MHz, DMSO-d 6 ) δ 171.6, 135.5, 126.8, 126.5, 115.3, 108.7, 79.9, 75.2, 38.0, Z-isomer; 1 H NMR (400 MHz, DMSO-d 6 ) S2
3 δ (s, 1H), 8.08 (s, 1H), 7.06 (dd, J = 2.5, 1.8 Hz, 1H), 6.48 (dd, J = 3.7, 1.7 Hz, 1H), 6.14 (dd, J = 3.6, 2.8 Hz, 1H), 5.20 (d, J = 2.5 Hz, 2H), 3.40 (t, J = 2.5 Hz, 1H), 1.91 (s, 3H); 13 C NMR (101 MHz, DMSO-d 6 ) δ 165.0, 138.5, 126.5, 126.4, 114.7, 109.1, 79.7, 75.7, 37.1, 21.6.; IR (ATR, cm -1 ) 3248, 1675, 1427, 1390, 1348, 1125, 1031, 885, 726, 669, 548; HRMS for C 10 H 12 N 3 O [M+H] + : Found: N -((1-(Prop-2-yn-1-yl)-1H-pyrrol-2-yl)methylene)benzohydrazide (12c). Pyrrole aldehyde 9 (0.50 g, 3.76 mmol) and benzoyl hydrazide (0.51 g, 3.76 mmol) were reacted as described above. After evaporation of the solvent the residue was crystallized from CHCl 3 in petroleum ether atmosphere to give the product 12c as white crystals (0.55 g, 58%), mp C. 1 H NMR (400 MHz, DMSO-d 6 ) δ (s, 1H), 8.40 (s, 1H), 7.90 (dd, J = 7.1, 1.2 Hz, 2H), 7.58 (t, J = 7.2 Hz, 1H), 7.52 (t, J = 7.3 Hz, 2H), 7.12 (d, J = 1.8 Hz, 1H), 6.55 (dd, J = 3.6, 1.5 Hz, 1H), 6.18 (dd, J = 3.4, 3.0 Hz, 1H), 5.28 (d, J = 2.3 Hz, 2H), 3.43 (t, J = 2.3 Hz, 1H); 13 C NMR (101 MHz, DMSO-d 6 ) δ 162.6, 140.5, 133.6, 131.5, 128.4, 127.4, 126.7, 126.6, 115.1, 109.2, 79.7, 75.7, 37.1; IR (ATR, cm -1 ) 3289, 1646, 1602, 1559, 1397, 1279, 1124, 1060, 718, 685, 632; HRMS for C 15 H 14 N 3 O [M+H] + : Found: Methyl-N'-((1-(prop-2-yn-1-yl)-1H-pyrrol-2-yl)methylene)benzenesulfonohydrazide N O N S NH O (12d). Pyrrole aldehyde 9 (0.13 g, mmol) and p- toluenesulfonyl hydrazide (0.19 g, mmol) were reacted as described above. After evaporation of the solvent the residue was crystallized from CHCl 3 in petroleum ether atmosphere to give the product 12d as brownish crystals in quantitative yield (0.30 g, 100%, NMR yield), mp C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.16 (s, 1H), 7.86 (d, J = 8.3 Hz, 2H), 7.72 (s, 1H), 7.30 (d, J = 8.0 Hz, 2H), 7.02 (dd, J = Hz, 1H), 6.38 (dd, J = 3.8, 1.7 Hz, 1H), 6.14 (dd, J = 3.8, 2.8 Hz, 1H), 4.99 (d, J = 2.5 Hz, 2H), 2.40 (s, 3H), 2.37 (t, J = 2.6 Hz, 1H); 13 C NMR (101 MHz, CDCl 3 ) δ 144.3, 142.2, 135.3, 129.8, 128.2, 127.1, 125.7, 118.0, 109.4, 78.4, 73.9, 38.6, 21.7; IR (ATR, cm -1 ) 3248, 1540, 1395, 1355, 1308, 1161, 1020, 930, 804, 736, 659, 547, 526; HRMS for C 15 H 16 N 3 O 2 S [M+H] + : Found: (E/Z)-N'-((1-(prop-2-yn-1-yl)-1H-pyrrol-2-yl)methylene)thiophene-2-carbohydrazide N O N C NH S (12e). Pyrrole aldehyde 9 (0.27 g, 2.00 mmol) and thiophene-2- S3
4 carbohydrazide (0.28 g, 2.00 mmol) were reacted as described above. After evaporation of the solvent, the residue was crystallized from MeOH to give the product 12e as pale yellow needles and sponge crystals in quantitative yield (0.51 g, 100%, NMR yield). E-isomer 63%; Z-isomer 37%. E-isomer; 1 H NMR (400 MHz, DMSO-d 6 ) δ (s, 1H), 8.36 (s, 1H), 7.87 (d, J = 3.2 Hz, 1H), 7.85 (d, J = 4.9 Hz, 1H), (m, 1H), 7.11 (s, 1H), 6.56 (s, 1H), 6.18 (t, J = 3.0 Hz, 1H), 5.25 (s, 2H), 3.44 (s, 1H); 13 C NMR (101 MHz, DMSO-d 6 ) δ , 138.5, 136.7, 134.1, 134.0, 133.8, 126.4, 114.4, 109.2, 79.5, 76.2, 37.0; Z-isomer; 1 H NMR (400 MHz, DMSO-d 6 ) δ (s, 1H), 8.12 (s, 1H), 8.03 (s, 1H), 7.90 (d, J = 9.4 Hz, 1H), (m, 1H), 7.11 (s, 1H), 6.64 (s, 1H), 6.18 (t, J = 3.0 Hz, 1H), 5.15 (s, 2H), 3.48 (s, 1H); 13 C NMR (101 MHz, DMSO-d 6 ) δ 157.3, 140.3, 131.5, 128.5, 128.0, 126.8, 126.6, 115.2, 109.2, 79.7, 75.8, 37.2; IR (ATR, cm -1 ) 3225, 1624, 1558, 1520, 1416, 1328, 1299, 1132, 844, 804, 707; HRMS for C 13 H 12 N 3 OS [M+H] + : Found: N'-((1-(3-phenylprop-2-yn-1-yl)-1H-pyrrol-2-yl)methylene)benzohydrazide (12f). Pyrrole aldehyde 10 (209 mg, mmol) and benzoylhydrazine (136 mg, mmol) were reacted as described above. After evaporation of the solvent, the residue was crystallized from MeOH to give the product 12f as white crystals (298 mg, 91%), mp C. 1 H NMR (400 MHz, DMSO-d 6 ) δ (s, 1H), 8.47 (s, 1H), 7.92 (dd, J = 7.0, 1.4 Hz, 2H), 7.58 (t, J = 7.2 Hz, 1H), 7.52 (t, J = 7.2 Hz, 1H), 7.46 (dd, J = 7.2, 2.3 Hz, 2H), 7.37 (d, J = 1.6 Hz, 2H), 7.36 (d, J = 1.5 Hz, 2H), 7.23 (d, J = 1.8 Hz, 1H), 6.59 (dd, J = 3.6, 1.5 Hz, 1H), 6.21 (dd, J = 3.4, 2.9 Hz, 1H), 5.55 (s, 2H); 13 C NMR (101 MHz, DMSO-d 6 ) δ 162.7, 140.7, 133.6, 131.5, 128.8, 128.6, 128.4, 127.5, 126.8, 126.7, 121.8, 115.2, 109.2, 85.4, 84.2, 48.6, 37.9; IR (ATR, cm -1 ) 3212, 3053, 1644, 1614, 1543, 1464, 1346, 1289, 1077, 720, 693; HRMS for C 21 H 18 N 3 O [M+H] + : Found: N'-((1-(3-phenylprop-2-yn-1-yl)-1H-pyrrol-2-yl)methylene)thiophene-2-carbohydrazide (12g). Pyrrole aldehyde 10 (209 mg, mmol) and thiophene-2- carbohydrazide (142 mg, mmol) were reacted as described above. After evaporation of the solvent the residue was crystallized from MeOH to give the product 12g as pale yellow crystals (303 mg, 91%, crude yield), mp C. 1 H NMR (400 MHz, CDCl 3 ) δ 1 (s, 1H), 8.25 (s, 1H), 8.09 (s, 1H), 7.64 (s, 1H), 7.43 (d, J = 6.1 Hz, 2H), (m, 3H), 7.17 (s, 1H), 7.14 (s, 1H), 6.67 (s, 1H), 6.28 (s, 1H), 5.43 (s, 2H); 13 C NMR (101 MHz, CDCl 3 ) δ 163.0, 138.6, 135.1, 133.6, 133.4, (2C), 128.8, 128.4, S4
5 126.8, 126.5, 122.4, 117.6, 109.7, 86.0, 83.8, 39.4; IR (ATR, cm -1 ) 2875, 1637, 1514, 1423, 1399, 1281, 1223, 1070, 1028, 689, 645; HRMS for C 19 H 16 N 3 OS [M+H] + : Found: N'-((1-(3-phenylprop-2-yn-1-yl)-1H-pyrrol-2-yl)methylene)formohydrazide (12h). O Pyrrole aldehyde 10 (209 mg, mmol) and formohydrazide (60 mg, N NH H mmol) were reacted as described above. After evaporation, it was N re-crystallized from MeOH to give the product as brown crystals (221 mg, 88%, NMR yield), mp C. 1 H NMR (400 MHz, CDCl 3 ) δ (bs, 1H), 8.75 (d, J = 9.3 Hz, 1H), 7.88 (s, 1H), 7.44 (dd, J = 7.1, 2.2 Hz, 2H), 7.32 (m, 3H), 7.15 (bs, 1H), 6.52 (dd, J = 3.4, 1.2 Hz), 6.23 (t, J = 3.1 Hz), 5.34 (s, 2H); 13 C NMR (101 MHz, CDCl 3 ) δ 165.6, 139.7, 131.9, 128.7, 128.5, 126.9, 126.0, 122.4, 117.6, 109.3, 85.7, 83.6, 39.6; IR (ATR, cm -1 ) 1684, 1425, 1359, 1283, 1219, 1172, 1115, 751, 716, 687; HRMS for C 15 H 14 N 3 O [M+H] + : Found: General Procedure for pyrrole-fused C,Nˈ-cyclic azomethine imine derivatives 13a-h. Hydrazone 12a-h (0.10 g, 0.53 mmol) and 5 mole % CF 3 SO 3 Ag were stirred in 3 ml of CHCl 3 at room temperature for 3 hours. The solvent was evaporated to give the desired cyclization products 13a-h. (3-Methylpyrrolo[1,2-a]pyrazin-2-ium-2-yl)(formyl)amide (13a) Hydrazone 12a (0.10 g, NCHO 0.57 mmol) was reacted as described above to give dark red oily N compund (0.10 g, 89%, NMR yield). 1 H NMR (400 MHz, CDCl 3 ) δ N CH (s, 1H), 8.19 (d, J = 1.7 Hz, 1H), 8.00 (s, 1H), 7.74 (s, 1H), 7.20 (dd, J = 3.3, 1.0 Hz, 1H), (m, 1H), 2.46 (s, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 191.5, 165.2, 139.4, 130.0, 125.8, 120.1, 118.5, 112.2, 15.8; IR (ATR, cm -1 ) 2917, 1653, 1558, 1541, 1541, 1457, 1419, 1173, 1078, 718; HRMS for C 9 H 10 N 3 O [M+H] + : Found: Acetyl(3-methylpyrrolo[1,2-a]pyrazin-2-ium-2-yl)amide (13b) Hydrazone 12b (0.10 g, 0.53 mmol) was reacted as described above to give red dark oily compound (0.10 g, 99%, NMR yield). 1 H NMR (400 MHz, CDCl 3 ) δ 8.74 (s, 1H), 8.03 (s, 1H), 7.75 (s, 1H), 7.14 (d, J = 4.1 Hz, 1H), 7.05 (dd, J = 4.4, 2.4 Hz, 1H), 2.37 (s, 3H), 2.11 (s, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 173.9, 139.7, 130.2, 125.8, 120.5, 120.0, 118.5, 112.3, 22.2, 15.5; IR (ATR, cm -1 ) 1653, 1558, 1541, 1419, 1373, 1273, 1242, 719; HRMS for C 10 H 11 N 3 O [M+H] + : Found: S5
6 Benzoyl(3-methylpyrrolo[1,2-a]pyrazin-2-ium-2-yl)amide (13c). Hydrazone 12c (0.10 g, 0.40 mmol) was reacted as described above to give reddish oily compound (0.10 g, 100%, NMR yield). 1 H NMR (400 MHz, CDCl 3 ) δ 9.09 (s, 1H), (m, 2H), 7.94 (bs, 1H), 7.63 (bd, J = 2.1 Hz, 1H), (m, 3H), 7.11 (bd, A-part of AB-system, J = 4.4 Hz, 1H), 7.06 (dd, B-part of AB-system, J = 4.4, 2.4 Hz, 1H), 2.48 (s, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 171.0, 139.0, 137.6, 130.4, 130.1, 128.1, 128.0, 126.0, 119.2, 118.9, 118.4, 110.6, 15.8; IR (ATR, cm -1 ) 1653, 1558, 1370, 1246, 1160, 1028, 745, 636. (3-Methylpyrrolo[1,2-a]pyrazin-2-ium-2-yl)(tosyl)amide (13d). Hydrazone 12d (0.30 g, mmol) and 1 wt % AuCl 3 were stirred in 3 ml of CHCl 3 at room NTs N temperature for 3 hours. The solvent was evaporated to give the product N CH 13d as green powder (0.30 g, 100%, NMR yield), mp C. 1 3 H NMR (400 MHz, DMSO-d 6 ) δ 9.13 (s, 1H), 8.41 (d, J = 0.7 Hz, 1H), 8.04 (t, J = 1.2 Hz, 1H), (m, 3H), (m, 3H), 2.32 (s, 3H), 1.82 (s, 3H); 13 C NMR (101 MHz, DMSO-d 6 ) δ 141.6, 141.4, 140.4, 130.0, 129.2, 125.9, 125.6, 120.9, 119.5, 118.9, 112.2, 20.8, 15.0; IR (ATR, cm -1 ) 3079, 1653, 1558, 1424, 1268, 1136, 1083, 1039, 918, 753, 656, 535; HRMS for C 15 H 16 N 3 O 2 S [M+H] + : : Found (3-Methylpyrrolo[1,2-a]pyrazin-2-ium-2-yl)(thiophene-2-carbonyl)amide (13e) Hydrazone 12e (0.10 g, 0.39 mmol) was reacted as described above to give reddish oily compound (0.10 g, 90%, NMR yield). 1 H NMR (400 MHz, CDCl 3 ) δ 8.95 (s, 1H), 7.92 (s, 1H), 7.79 (d, J = 3.5 Hz, 1H), 7.67 (s, 1H), 7.34 (d, J = 4.9 Hz, 1H), 7.16 (d, J = 4.3 Hz, 1H), 7.09 (dd, J = 4.3, 2.4 Hz, 1H), 7.07 (dd, J = 4.7, 4.0 Hz, 1H), 2.44 (s, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 166.9, 140.0, 139.8, 130.3, 129.8, 128.6, 127.6, 125.8, 120.3, 120.0, 118.5, 112.4, 15.6; IR (ATR, cm -1 ) 3078, 1652, 1558, 1458, 1418, 1252, 1160, 1027, 717, 636; HRMS for C 13 H 12 N 3 OS [M+H] + : Found: Benzoyl(3-benzylpyrrolo[1,2-a]pyrazin-2-ium-2-yl)amide (13f) Hydrazone 12f (100 mg, 0.31 mmol) was reacted as described above to give dark red oily compound (79 mg, 78%). 1 H NMR (400 MHz, CDCl 3 ) δ 9.15 (s, 1H), 8.16 (d, J = 7.3 Hz, 2H), 7.55 (s, 1H), (m, 8H), 7.26 (d, J = 1.0 Hz, 1H), 7.16 (d, J = 4.0 Hz, 1H), 7.07 (dd, J = 3.9, 2.3 Hz, 1H), 4.25 (s, 2H); 13 C NMR (101 MHz, CDCl 3 ) δ 170.6, 139.6, 136.9, 135.6, 134.2, 130.5, 129.9, 129.2, 128.2, 128.1, 127.6, 125.7, 119.9, 119.6, 119.4, 111.4, 34.9; IR (ATR, cm -1 ) 3062, S6
7 2919, 1653, 1527, 1343, 1281, 1252, 1155, 1028, 696; HRMS for C 21 H 18 N 3 O [M+H] + : Found: (3-Benzylpyrrolo[1,2-a]pyrazin-2-ium-2-yl)(thiophene-2-carbonyl)amide (13g) Hydrazone 12g (50 mg, 0.15 mmol) was reacted as described above. After evaporation of the solvent, the column chromatography was carried out on silica gel (10 g) eluting with hexane/etoac (1:1) followed by EtOAc to give 13g as dark red oily compund (27 mg, 54%, NMR yield). 1 H NMR (400 MHz, CDCl 3 ) δ 8.88 (s, 1H), 7.69 (d, J = 2.8 Hz, 1H), 7.52 (s, 1H), 7.37 (s, 1H), (m, 7H), 6.96 (dd, J = 4.4, 2.3 Hz, 1H), 6.94 (dd, J = 4.8, 3.9 Hz, 1H), 4.05 (s, 2H); 13 C NMR (101 MHz, CDCl 3 ) δ 165.7, 140.7, 134.9, 133.9, 130.2, 129.8, 129.5, 129.5, 129.2, 127.8, 127.7, 125.6, 121.6, 120.6, 119.4, 113.6, 34.7; IR (ATR, cm -1 ) 2916, 1653, 1579, 1510, 1415, 1314, 1280, 1208, 1028, 719, 703; HRMS for C 19 H 16 N 3 OS [M+H] + : Found: (3-Benzylpyrrolo[1,2-a]pyrazin-2-ium-2-yl)(formyl)amide (13h) Hydrazone 12h (50 mg, 0.20 mmol) was reacted as described above. After evaporation of the solvent, the column chromatography was carried out on 10 g silica gel eluting with hexane/etoac (1:1) followed by EtOAc to give dark red oily compound 13h (47 mg, 93%, NMR yield). 1 H NMR (400 MHz, CDCl 3 ) δ 8.98 (s, 1H), 8.17 (s, 1H), 7.54 (s, 1H), (m, J = 6.9 Hz, 6H), 7.17 (d, J = 4.3 Hz, 1H), 7.07 (dd, J = 4.4, 2.4 Hz, 1H), 4.20 (s, 2H); 13 C NMR (101 MHz, CDCl 3 ) δ 175.5, 164.8, 140.0, 134.7, 133.7, 130.0, 129.4, 127.9, 125.6, 121.4, 120.7, 119.5, 34.7; IR (ATR, cm -1 ) 2919, 1676, 1654, 1492, 1355, 1256, 1074, 1028, 725, 697; HRMS for C 15 H 14 N 3 O [M+H] + : Found: General Procedure for Cycloaddition Reactions: Synthesis of Dipolaphile (1 mmol) was added to a solution of (3-methylpyrrolo[1,2-a]pyrazin-2-ium-2-yl)(tosyl)amide (13d) (1 mmol) in 15 ml of toluene. The resulting mixture was heated at the reflux temperature for 18 h. After cooling to room temperature, the solvent was evaporated under the reduced pressure. The crude product was purified over silica gel eluting with hexane/etoac (10:1 2:1) to give the product. 5-Methylpyrazolo[1,5-a]pyrrolo[2,1-c]pyrazine-1-carbonitrile (14) (3-Methylpyrrolo[1,2- a]pyrazin-2-ium-2-yl)(tosyl)amide (13d) (140 mg, 0.46 mmol) and S7
8 acrylonitrile (30 µl, 0.46 mmol) were reacted as described above. White needles from chloroform/hexane (40 mg, 44%), mp.: C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.03 (s, 1H), 7.30 (bs, 1H), 7.27 (dd, J = 2.7, 1.3 Hz, 1H), 7.18 (bd, J = 4.0 Hz, 1H), 6.76 (dd, J = 4.0, 2.7 Hz, 1H), 2.58 (d, J = 1.2 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 143.1, 136.4, 122.0, 120.0, 116.8, 114.1, 113.8, 112.0, 105.3, 83.3, 14.7; IR (KBr, cm-1) 3100, 2223, 1587, 1443, 1421, 989, 882, 824, 728, 710, 644; HRMS for C 11 H 9 N 4 [M+H] + : calculated , found: HRMS for C 11 H 9 N 4 [M+H] + : Found: Methylpyrazolo[1,5-a]pyrrolo[2,1-c]pyrazine-1-carbaldehyde (15) (3- Methylpyrrolo-[1,2-a]pyrazin-2-ium-2-yl)(tosyl)amide (13d) (150 mg, 0.5 mmol) and acrolein (33 µl, 0.5 mmol) were reacted as described above. The crude product was purified over silica gel eluting with hexane/etoac (5:1 2:1) to give 15. White powder from (50 mg, 50%) mp C. 1 H- NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.23 (s, 1H), 7.69 (d, J = 4.0 Hz, 1H), 7.33 (s, 1H), 7.30 (dd, J = 2.6, 1.4 Hz, 1H), 6.75 (dd, J = 4.0, 2.6 Hz, 1H), 2.59 (d, J = 1.1 Hz, 3H); 13 C- NMR (101 MHz, CDCl 3 ) δ 182.9, 144.3, 133.4, 121.4, 121.3, , 116.2, 113.3, 112.1, , 14.9; IR (KBr, cm -1 ) 3101, 1661, 1565, 1532, 1360, 1235, 805, 726, 645; HRMS for [M+H] + : C 11 H 10 N 3 O Found: Methyl 5-methylpyrazolo[1,5-a]pyrrolo[2,1-c]pyrazine-1-carboxylate (16) (3-Methyl-pyrrolo-[1,2-a]pyrazin-2-ium-2-yl)(tosyl)amide (13d) (150 mg, 0.5 mmol) and acrolein (50 µl, 0.5 mmol) were reacted as described above. The crude product was purified over silica gel eluting with hexane/etoac (10:1 3:1) to give 16. White needles, (50 mg, 44%) from diethyl ether, mp C. 1 H-NMR (400 MHz, CDCl 3 ) δ 8.20 (s, 1H), 7.70 (ddd, J = 4.0, 1.4, 0.7 Hz, 1H), 7.23 (bs, 1H), 7.22 (dd, J = 2.6, 1.4 Hz, 1H), 6.70 (dd, J = 4.0, 2.6 Hz, 1H), 3.93 (s, 3H), 2.55 (d, J = 1.2 Hz, 3H); 13 C-NMR (101 MHz, CDCl 3 ) δ , 143.2, 134.4, 121.7, 121.3, 116.6, 112.9, 111.5, 108.8, 106.0, 51.4, 14.9; IR (KBr, cm - 1) 2923, 1713, 1578, 1535, 1422, 1266, 1246, 1130, 1050, 992, 769, 701, 625; HRMS for C 12 H 12 N 3 O 2 [M+H] + : Found: Dimethyl 5-methylpyrazolo[1,5-a]pyrrolo[2,1-c]pyrazine-1,2-dicarboxylate (17) (3- Methyl-pyrrolo-[1,2-a]pyrazin-2-ium-2-yl)(tosyl)amide (13d) (170 mg, 0.56 mmol) and dimethyl acetylenedicarboxylate (71 µl, 0.56 mmol) were reacted as described above. The crude product was purified over silica gel eluting with hexane/etoac (10:1 2:1). S8
9 White crystals from chloroform in petroleum ether atmosphere (60 mg, 37%), mp C. 1 H-NMR (400 MHz, CDCl 3 ) δ 7.54 (bd, J = 3.9 Hz, 1H), 7.31 (bs, 1H), 7.24 (dd, J = 2.7, 1.4 Hz, 1H), 6.71 (dd, J = 3.9, 2.7 Hz, 1H), 4.00 (s, 3H), 3.94 (s, 3H), 2.57 (d, J = 0.9 Hz, 3H); 13 C-NMR (101 MHz, CDCl 3 ) δ 163.8, 162.9, 145.9, 134.8, 121.6, 120.6, 117.1, 113.1, 112.7, 109.0, 105.1, 53.0, 52.0, 14.8; IR (KBr, cm -1 ) 2956, 1707, 1566, 1436, 1422, 1353, 1267,1183, 1072, 771, 732; HRMS for C 14 H 13 N 3 NaO 4 [M+Na] + : Found: S9
10 NMR Spectra N O H N C NH N O H N C NH Figure 1. 1 H and 13 C NMR Spectra of 12a in CDCl 3 (400 MHz) S10
11 Figure 2. 1 H and 13 C NMR Spectra of 12b in DMSO (400 MHz) S11
12 N O N C NH N O N C NH Figure 3. 1 H and 13 C NMR Spectra of 12c in DMSO (400 MHz) S12
13 N O N S NH O N O N S NH O Figure 4. 1 H and 13 C NMR Spectra of 12d in CDCl 3 (400 MHz) S13
14 Figure 5. 1 H and 13 C NMR Spectra of 12e in DMSO (400 MHz) S14
15 Figure 6. 1 H and 13 C NMR Spectra of 12f in DMSO (400 MHz) S15
16 Figure 7. 1 H and 13 C NMR Spectra of 12g in CDCl 3 (400 MHz) S16
17 Figure 8. 1 H and 13 C NMR Spectra of 12h in CDCl 3 (400 MHz) S17
18 Figure 9. 1 H and 13 C NMR Spectra of 13a in CDCl 3 (400 MHz) S18
19 Figure H and 13 C NMR Spectra of 13b in CDCl 3 (400 MHz) S19
20 N O N C N N O N C N Figure H and 13 C NMR Spectra of 13c in CDCl 3 (400 MHz) S20
21 Figure H and 13 C NMR Spectra of 13d in DMSO (400 MHz) S21
22 Figure H and 13 C NMR Spectra of 13e in CDCl 3 (400 MHz) S22
23 Figure H and 13 C NMR Spectra of 13f in CDCl 3 (400 MHz) S23
24 Figure H and 13 C NMR Spectra of 13g in CDCl 3 (400 MHz) S24
25 Figure H and 13 C NMR Spectra of 13h in CDCl 3 (400 MHz) S25
26 Figure 17: 1 H and 13 C NMR Spectra of 14 in CDCl 3 (400 MHz) S26
27 f1 (ppm) f1 (ppm) Figure 18: 1 H and 13 C NMR Spectra of 15 in CDCl 3 (400 MHz) S27
28 f1 (ppm) Figure 19: DEPT 90 and DEPT 135 Spectra of 14 in CDCl 3 (400 MHz) S28
29 Figure 20: COSY and HSQC Spectra of 15 in CDCl 3 (400 MHz) S29
30 Figure 21: HMBC Spectra of 15 in CDCl 3 (400 MHz) S30
31 Figure 22: 1 H and 13 C NMR Spectra of 16 in CDCl 3 (400 MHz) S31
32 Figure 23: 1 H and 13 C NMR Spectra of 17 in CDCl 3 (400 MHz) S32
33 THEORETICAL CALCULATIONS 1. Methodology The quantum chemical calculations were performed using the Gaussian 09 program package 1 and the structures were fully optimized at the RHF/6-311 G(d,p) level of theory without constraints. NICS values were computed on the basis of RHF/6-311 G(d,p) geometries of molecules using the gaugeincluding atomic orbital (GIAO) method at the RHF/6-311 G(d,p) theory level. 1b-d Coordinates for 13a Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z C C C C N H H H C C H C C H H H N N H C O H Coordinates for 13c Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z C C C C N S33
34 6 1 H H H C C H C C H H H N N H C O C C C C H C H C H H H Coordinates for 13d Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z C C C C N H H H C C H C C H H H N S34
35 18 7 N S C C C C H C H C H H C H H H O O H Coordinates 13f Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z C C C C N H H H C C H C C H H N N H C O C C C C H S35
36 26 6 C H C H H H C C C C H C H C H H H Coordinates for 14 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z C C C C C C C H H H H C H H H N N C C N H C N Coordinates for 15 S36
37 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z C C C C C C C H H H H C H H H N N C C N H C H O Coordinates for 16 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z C C C C C C C H H H H C H H H N N S37
38 18 6 C C N H C O O H Coordinates for 17 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z C C C C C C C H H H H C H H H N N C C N C O O C O O C H H H C H H H Coordinates for 23 S38
39 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z C C C C N H H H H H Coordinates for 24 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z C C C N H H H H N Coordinates for 25 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z C C N C C N H H H H S39
40 X-Ray structure determination of 13d For the crystal structure determination, single-crystal of compound 13d was used for data collection on a four-circle Rigaku R-AXIS RAPID-S diffractometer (equipped with a twodimensional area IP detector). Graphite-monochromated Mo-K α radiation (λ = Å) and oscillation scans technique with w = 5º for one image were used for data collection. The lattice parameters were determined by the least-squares methods on the basis of all reflections with F 2 > 2σ(F 2 ). Integration of the intensities, correction for Lorentz and polarization effects and cell refinement was performed using CrystalClear (Rigaku/MSC Inc.,2005) software. 2 The structures were solved by direct methods using SHELXS-97 3 and refined by a full-matrix least-squares procedure using the program SHELXL All nonhydrogen atoms were refined anisotropically and H atoms were positioned geometrically and refined using a riding model. The final difference Fourier maps showed no peaks of chemical significance. Crystal data for 13d: C 15 H 15 N 3 O 2 S, crystal system, space group: triclinic, P-1; (no:2); unit cell dimensions: a = (2), b = (3), c = (4) Å, α= (1), β = (2), γ = (1) Å; volume: (5) Å 3 ; Z = 2; calculated density: 1.39 g/cm 3 ; absorption coefficient: mm -1 ; F(000): 316; θ-range for data collection º ; refinement method: full matrix least-square on F 2 ; data/parameters: 2009/192; goodness-of-fit on F 2 : 1.031; final R-indices [I > 2σ(I)]: R 1 = 0.047, wr 2 = 0.106; largest diff. peak and hole: and e Å -3. S40
41 Fig. 1. Up: Mercury drawing of the molecule 13d. Thermal ellipsoids are drawn at the 50% probability level. Selected bond lengths (Å) ; S1-O (2), S1-O (2), S1-C (2), S1-N (2), N3-N (3), N2-C (3), N2-C (3), N1-C (3). Down: C-H N interaction along the a-axis Crystallographic data that were deposited in CSD under CCDC registration number contain the supplementary crystallographic data for this Letter. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre (CCDC) via S41
42 and are available free of charge upon request to CCDC, 12 Union Road, Cambridge, UK (fax: , References References (1) (a) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.;Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision A.02; Gaussian, Inc.: Wallingford, CT, (b) Becke, A. D. J. Chem. Phys. 1993, 98, 5648; (c) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785; (d) Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H. Chem. Phys. Lett. 1989, 157, 200. (2) Rigaku/MSC, Inc.: 9009 new Trails Drive, The Woodlands, TX (3) Sheldrick, G. M. SHELXS97 and SHELXL97; University of Göttingen: Germany, S42
Structural Expression of Exo-Anomeric Effect
Supporting Information for Structural Expression of Exo-Anomeric Effect Elena R. Alonso, Isabel Peña, Carlos Cabezas, and José L. Alonso* Contents Table S1: Transition frequencies of conformer cc-β- 4
Διαβάστε περισσότεραSupporting Information. DFT Study of Pd(0)-Promoted Intermolecular C H Amination with. O-Benzoyl Hydroxylamines. List of Contents
Supporting Information DFT Study of Pd(0)-Promoted Intermolecular C H Amination with O-Benzoyl Hydroxylamines Yunfei Zhou and Xiaoguang Bao* College of Chemistry, Chemical Engineering and Materials Science,
Διαβάστε περισσότεραEthyl Nitroacetate in Aza-Henry Addition on Trifluoromethyl Aldimines: A Solvent-Free Procedure To Obtain Chiral Trifluoromethyl α,β-diamino Esters
Supporting Information Ethyl Nitroacetate in Aza-Henry Addition on Trifluoromethyl Aldimines: A Solvent-Free Procedure To Obtain Chiral Trifluoromethyl α,β-diamino Esters Luca Parise, Alessia Pelagalli,
Διαβάστε περισσότεραBifunctional Water Activation for Catalytic Hydration of Organonitriles
Supporting Information (16 pages including the cover page) Bifunctional Water Activation for Catalytic Hydration of Organonitriles Prosenjit Daw, Arup Sinha, S. M. Wahidur Rahaman, Shrabani Dinda and Jitendra
Διαβάστε περισσότεραEnantioselective 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 περισσότεραSupporting Information. A single probe to sense Al(III) colorimetrically and. Cd(II) by turn-on fluorescence in physiological
Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2015 Supporting Information A single probe to sense Al(III) colorimetrically and Cd(II) by
Διαβάστε περισσότεραElectronic Supplementary Material (ESI) for Chemical Communications This journal is The Royal Society of Chemistry 2013
General. All manipulations were carried out under an inert atmosphere of dry nitrogen using standard Schlenk techniques or in an inert-atmosphere glove-box. Solvents were dried form the appropriate drying
Διαβάστε περισσότεραSupporting Information. Identification of Absolute Helical Structures of Aromatic Multi-layered Oligo(m-phenylurea)s in Solution.
Supporting Information Identification of Absolute Helical Structures of Aromatic Multi-layered Oligo(m-phenylurea)s in Solution. Mayumi Kudo, 1 Takayuki Hanashima, 2 Atsuya Muranaka, 3,* Hisako Sato, 4,5,
Διαβάστε περισσότεραStriking Difference between Succinimidomethyl and Phthalimidomethyl Radicals in Conjugate Addition to Alkylidenemalonate Initiated by Dimethylzinc
Striking Difference between Succinimidomethyl and Phthalimidomethyl Radicals in Conjugate Addition to Alkylidenemalonate Initiated by Dimethylzinc Ken-ichi Yamada*, Yusuke Matsumoto, Shintaro Fujii, Takehito
Διαβάστε περισσότεραSupporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2006
Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2006 Supporting information Chiral Thiourea-Based Bifunctional Organocatalysts in the Asymmetric Nitro- Michael Addition:
Διαβάστε περισσότεραElectronic Supplementary Information
Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2015 Electronic Supplementary Information to the paper Theoretical Insights into the Separation
Διαβάστε περισσότεραSupporting Information for
Supporting Information for Hydrogen-Bridged Digermyl and Germylsilyl Cations N. Kordts, C. Borner, R. Panisch, W. Saak, T. Müller* Contents. 1. Computational Details 2. IR Spectroscopic Results 3. NMR-Spectroscopic
Διαβάστε περισσότεραAlkyl-functionalization of 3,5-bis(2-pyridyl)-1,2,4,6- thiatriazine
Electronic Supplementary Material (ESI) for New Journal of Chemistry. This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016 Electronic Supporting Information
Διαβάστε περισσότεραSyntheses and Characterizations of Molecular Hexagons and Rhomboids and Subsequent Encapsulation of Keggin-Type Polyoxometalates by Molecular Hexagons
Supporting Information for Syntheses and Characterizations of Molecular Hexagons and Rhomboids and Subsequent Encapsulation of Keggin-Type Polyoxometalates by Molecular Hexagons Kazuhiro Uehara, Takamichi
Διαβάστε περισσότεραSupporting 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 περισσότεραPhotostimulated Reduction of Nitriles by SmI 2. Supporting information
Photostimulated Reduction of Nitriles by SmI 2 Chintada Nageswara Rao and Shmaryahu Hoz * Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel E-mail: shoz@mail.biu.ac.il Supporting information
Διαβάστε περισσότεραElectronic Supplementary Information
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2017 Electronic Supplementary Information Hydrolysis of cis- and transplatin: structure and reactivity
Διαβάστε περισσότεραSupporting Information. Fluorinated Thiophene-Based Synthons: Polymerization of 1,4-Dialkoxybenzene
Supporting Information Fluorinated Thiophene-Based Synthons: Polymerization of 1,4-Dialkoxybenzene and Fluoro-Dithieno-2,1,3-benzothiadiazole by Direct Heteroarylation Carl Roy, 1 Thomas Bura, 1, Serge
Διαβάστε περισσότεραDiels-Alder reaction of acenes with singlet and triplet oxygen - theoretical study of two-state reactivity
Supporting Information Diels-Alder reaction of acenes with singlet and triplet oxygen - theoretical study of two-state reactivity A. Ravikumar Reddy and Michael Bendikov* Computational details: Density
Διαβάστε περισσότεραRhodium-Catalyzed Direct Bis-cyanation of. Arylimidazo[1,2-α]pyridine via Double C-H Activation
Supporting Information Rhodium-Catalyzed Direct Bis-cyanation of Arylimidazo[1,2-α]pyridine via Double C-H Activation Xinju Zhu, Xiao-Jing Shen, Zi-Yao Tian, Shuai Lu, Lu-Lu Tian, Wen-Bo Liu, Bing Song,*
Διαβάστε περισσότεραSupporting Information. Palladium Complexes with Bulky Diphosphine. Synthesis of (Bio-) Adipic Acid from Pentenoic. Acid Mixtures.
Supporting Information Palladium Complexes with Bulky Diphosphine Ligands as Highly Selective Catalysts for the Synthesis of (Bio-) Adipic Acid from Pentenoic Acid Mixtures. Choon Heng Low, James D. Nobbs,*
Διαβάστε περισσότεραSupporting Information for. Catalytic C H α-trifluoromethylation of α,β-unsaturated Carbonyl Compounds
Supporting Information for Catalytic C H α-trifluoromethylation of α,β-unsaturated Carbonyl Compounds Zhongxue Fang, a Yongquan Ning, a Pengbing Mi, a Peiqiu Liao, a Xihe Bi* a,b a Department of Chemistry,
Διαβάστε περισσότεραSupporting 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 περισσότεραDirect 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 περισσότεραSupporting Information
Supporting Information Tris(pyrazolyl)methanides of the Alkaline Earth Metals - Influence of the Substitution Pattern on Stability and Degradation Christoph Müller, Alexander Koch, Helmar Görls, Sven Krieck,
Διαβάστε περισσότεραNaphthotetrathiophene Based Helicene-like Molecules: Synthesis and Photophysical Properties
Supporting information for: Naphthotetrathiophene Based Helicene-like Molecules: Synthesis and Photophysical Properties Xueqian Zhao 1, Lipeng Zhang 1, Jinsheng Song 1, *, Yuhe Kan 2, and Hua Wang 1, *
Διαβάστε περισσότεραIntermolecular Aminocarbonylation of Alkenes using Cycloadditions of Imino-Isocyanates. Supporting Information
Intermolecular Aminocarbonylation of Alkenes using Cycloadditions of Imino-Isocyanates Amanda Bongers, Christian Clavette, Wei Gan, Serge I. Gorelsky, Lyanne Betit, Kaitlyn Lavergne, Thomas Markiewicz,
Διαβάστε περισσότεραA Selective, Sensitive, Colorimetric and Fluorescence Probe. for Relay Recognition of Fluoride and Cu (II) ions with
Supporting Information for A Selective, Sensitive, Colorimetric and Fluorescence Probe for Relay Recognition of Fluoride and Cu (II) ions with OFF-ON-OFF Switching in Ethanol-Water Solution Yu Peng,* Yu-Man
Διαβάστε περισσότεραMild Aliphatic and Benzylic hydrocarbon C H Bond Chlorination Using Trichloroisocyanuric Acid (TCCA)
Mild Aliphatic and Benzylic hydrocarbon C H Bond Chlorination Using Trichloroisocyanuric Acid (TCCA) Sascha H. Combe, Abolfazl Hosseini, Alejandro Parra, # and Peter R. Schreiner*, Institute of Organic
Διαβάστε περισσότεραA 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 περισσότεραAsymmetric H/D exchange reaction of fluorinated aromatic ketones
Asymmetric H/D exchange reaction of fluorinated aromatic ketones Yujun Zhao 1 Xiaozhi Lim 2 Yuanhang Pan 1 Lili Zong 1 Wei Feng 1 and Choon-Hong Tan 1 * Kuo-Wei Huang 2 * 1 Department of Chemistry and
Διαβάστε περισσότεραNesting Complexation of C 60 with Large, Rigid D 2 Symmetrical Macrocycles
Supporting Information for: Nesting Complexation of C 60 with Large, Rigid D 2 Symmetrical Macrocycles Marco Caricato, a Carmine Coluccini, a Daniele Dondi, b Douglas Vander Griend, c and Dario Pasini,
Διαβάστε περισσότεραSupporting Information
Electronic Supplementary Material (ESI) for New Journal of Chemistry. This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2018 Supporting Information A Possible
Διαβάστε περισσότεραThe 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 περισσότεραNickel and Platinum PCP Pincer Complexes Incorporating an Acyclic Diaminoalkyl Central Moiety Connecting Imidazole or Pyrazole Rings
ickel and Platinum PCP Pincer Complexes Incorporating an Acyclic Diaminoalkyl Central Moiety Connecting Imidazole or Pyrazole Rings Braulio M. Puerta Lombardi, Rudy M. Braun, Chris Gendy, Chia Yun Chang,
Διαβάστε περισσότεραReaction of Lithium Diethylamide with an Alkyl Bromide and Alkyl Benzenesulfonate: Origins of Alkylation, Elimination, and Sulfonation.
Reaction of Lithium Diethylamide with an Alkyl omide and Alkyl Benzenesulfonate: rigins of Alkylation, Elimination, and ulfonation. Lekha Gupta, Antonio Ramírez and David B. Collum* Contribution from the
Διαβάστε περισσότεραCopper-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 περισσότεραSupporting 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 περισσότεραPush-Pull Type Porphyrin Based Sensitizers: The Effect of Donor Structure on the Light- Harvesting Ability and Photovoltaic Performance
Push-Pull Type Porphyrin Based Sensitizers: The Effect of Donor Structure on the Light- Harvesting Ability and Photovoltaic Performance Item Type Article Authors Qi, Qingbiao; Li, Renzhi; Luo, Jie; Zheng,
Διαβάστε περισσότεραSupporting 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 περισσότεραTitle N-H versus C-H Activation of a Pyrrole Imine at {Cp*Ir}: A Computational and Experimental Study
Supporting Information for: Title N-H versus C-H Activation of a Pyrrole Imine at {Cp*Ir}: A Computational and Experimental Study David L. Davies,* a Steven M. A. Donald, b Omar Al-Duaij, a John Fawcett,
Διαβάστε περισσότεραSupporting Information
Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2016 Supporting Information Luminescent Organoboron Ladder Compounds via Directed Electrophilic
Διαβάστε περισσότεραSupporting Information File 2. Crystallographic data of syn-bis-quinoxaline, 16c CH 3 CO 2 C 2 H 5 ;
Supporting Information File 2 Crystallographic data of syn-bis-quinoxaline, 16c CH 3 CO 2 C 2 H 5 ; Preparation, structures and host guest chemistry of fluorinated syn-bisquinoxaline molecular tweezers
Διαβάστε περισσότεραElectronic Supplementary Information (ESI) for
Electronic Supplementary Material (ESI) for Chemical Science. This journal is The Royal Society of Chemistry 2014 Electronic Supplementary Information (ESI) for A Kinetically Blocked 1,14:11,12- Dibenzopentacene:
Διαβάστε περισσότεραSupplementary Figures
Supplementary Figures Supplementary Figure 1. 1 H NMR spectrum (400 MHz, CDCl 3 ) of diester 3. Supplementary Figure 2. 13 C NMR spectrum (100 MHz, CDCl 3 ) of diester 3. 1 Supplementary Figure 3. 1 H
Διαβάστε περισσότεραSupplementary Material
Supplementary Material Synthesis of bis-oxathiaaza[3.3.3]propellanes via nucleophilic addition of (1,ω-alkanediyl)bis(N'-organylthioureas) on dicyanomethylene-1,3-indanedione Alaa A. Hassan, a * Kamal
Διαβάστε περισσότεραSUPPORTING INFORMATION. Visible Light Excitation of a Molecular Motor with an Extended Aromatic Core
SUPPORTING INFORMATION Visible Light Excitation of a Molecular Motor with an Extended Aromatic Core Thomas van Leeuwen, Jasper Pol, Diederik Roke, Sander J. Wezenberg, Ben L. Feringa* Stratingh Institute
Διαβάστε περισσότεραSupporting 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 περισσότεραSupporting 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 περισσότεραPyrrolo[2,3-d:5,4-d']bisthiazoles: Alternate Synthetic Routes and a Comparative Study to Analogous Fused-ring Bithiophenes
SUPPORTING INFORMATION Pyrrolo[2,3-d:5,4-d']bisthiazoles: Alternate Synthetic Routes and a Comparative Study to Analogous Fused-ring Bithiophenes Eric J. Uzelac, Casey B. McCausland, and Seth C. Rasmussen*
Διαβάστε περισσότεραCopper-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 περισσότεραSupporting Information
Supporting Information Vinylogous elimination/heck coupling/allylation domino reactions: access to 2- substituted 2,3-dihydrobenzofurans and indolines Jianguo Yang, *, Hanjie Mo, Xiuxiu Jin, Dongdong Cao,
Διαβάστε περισσότεραElectronic Supplementary Information (ESI)
Electronic Supplementary Information (ESI) Oleonin, the first secoiridoid with 1 -configuration from Ligustrum lucidum Xiao-Jun Huang, a,b,c Lei Wang, a,c Meng Shao, d Shu-Zhi Hu, a Ren-Wang Jiang, a Xin-Sheng
Διαβάστε περισσότεραPhoto-Induced Self-Assembly of Pt(II)-Linked Rings and Cages via the Photolabilization of a Pt(II) Pyridine Bond
Photo-Induced Self-Assembly of Pt(II)-Linked Rings and Cages via the Photolabilization of a Pt(II) Pyridine Bond Ken-ichi Yamashita, Kei-ichi Sato, Masaki Kawano and Makoto Fujita* Contents; Figure S1.
Διαβάστε περισσότεραSupporting 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 περισσότεραSupporting Information for:
Electronic Supplementary Material (ESI) for Chemical Science. This journal is The Royal Society of Chemistry 2018 Supporting Information for: Cation p interactions in protein-ligand binding: theory and
Διαβάστε περισσότεραPalladium-Catalyzed Direct ortho-sulfonylation of. Azobenzenes with Arylsulfonyl Chlorides via C H. Table of Contents
Electronic upplementary Material (EI) for RC Advances. This journal is The Royal ociety of Chemistry 205 upporting Information Palladium-Catalyzed Direct ortho-ulfonylation of Azobenzenes with Arylsulfonyl
Διαβάστε περισσότεραFigure S12. Kinetic plots for the C(2)-H/D exchange reaction of 2 CB[7] as a function
Supporting Information Encapsulation of Vitamin B 1 and its Phosphate Derivatives by Cucurbit[7]uril: Tunability of the Binding Site and Affinity by the Presence of Phosphate Groups Shengke Li, Hang Yin,
Διαβάστε περισσότεραHighly 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 περισσότεραSupporting Information
Electronic Supplementary Material (ESI) for New Journal of Chemistry. This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017 Supporting Information Synthesis
Διαβάστε περισσότεραSupporting 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 περισσότεραElectronic Supplementary Information
7- Selenabicyclo[2.2.1]heptane Phoebe E. Macdougall, a,b Heather M. Aitken, a,b Peter J. Scammells, a,c Yvonne Kavanagh, a,b Sara H. Kyne, a,b,d and Carl H. Schiesser* a,b Electronic Supplementary Information
Διαβάστε περισσότεραSupporting Information
Supporting Information Intramolecular Charge-Transfer Interaction of Donor Acceptor Donor Arrays Based on Anthracene Bisimide Tetsuo Iwanaga, *, Marina Ogawa, Tomokazu Yamauchi, and Shinji Toyota *, Department
Διαβάστε περισσότεραSynthesis and spectroscopic properties of chial binaphtyl-linked subphthalocyanines
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Synthesis and spectroscopic properties of chial binaphtyl-linked subphthalocyanines Luyang Zhao,
Διαβάστε περισσότεραSUPPORTING INFORMATION
Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2018 SUPPORTING INFORMATION Bulky cationic ß-diketiminate magnesium complexes Alexander Friedrich,
Διαβάστε περισσότεραPatrycja Miszczyk, Dorota Wieczorek, Joanna Gałęzowska, Błażej Dziuk, Joanna Wietrzyk and Ewa Chmielewska. 1. Spectroscopic Data.
; doi:10.3390/molecules22020254 S1 of S23 Supplementary Materials: Reaction of 3-Amino-1,2,4-Triazole with Diethyl Phosphite and Triethyl Orthoformate: Acid-Base Properties and Antiosteoporotic Activities
Διαβάστε περισσότεραchlorostibine Iou-Sheng Ke and François P. Gabbai Department of Chemistry, Texas A&M University, College Station, TX
σ-donor/acceptor confused ligands: The case of a chlorostibine Iou-Sheng Ke and François P. Gabbai Department of Chemistry, Texas A&M University, College Station, TX 77843-3255. *To whom correspondence
Διαβάστε περισσότεραAccessory Publication
Accessory Publication Pitfalls in the Photoelectron Spectroscopic Investigations of Benzyne. Photoelectron Spectrum of Cyclopentadienylideneketene. Anna Chrostowska, A,C Genevieve Pfister-Guillouzo, A
Διαβάστε περισσότεραSupporting Information. Pd(0)-Catalyzed Decarboxylative Coupling and Tandem C H Arylation/Decarboxylation for the. Synthesis of Heteroaromatic Biaryls
Supporting Information Pd()-Catalyzed Decarboxylative Coupling and Tandem C H Arylation/Decarboxylation for the Synthesis of Heteroaromatic Biaryls Debkumar andi, Yang-Ming Jhou, Jhen-Yi Lee, Bing-Chiuan
Διαβάστε περισσότεραSynthesis, characterization and luminescence studies of
Supporting Information for Synthesis, characterization and luminescence studies of gold(i) HC amide complexes Adrián Gómez-Suárez, David J. elson, David G. Thompson, David B. Cordes, Duncan Graham, Alexandra
Διαβάστε περισσότεραSupporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2008
Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2008 Organocatalytic Asymmetric Hydrophosphination of α,β- Unsaturated Aldehydes: Development, Mechanism and DFT Calculations
Διαβάστε περισσότεραIV. ANHANG 179. Anhang 178
Anhang 178 IV. ANHANG 179 1. Röntgenstrukturanalysen (Tabellen) 179 1.1. Diastereomer A (Diplomarbeit) 179 1.2. Diastereomer B (Diplomarbeit) 186 1.3. Aldoladdukt 5A 193 1.4. Aldoladdukt 13A 200 1.5. Aldoladdukt
Διαβάστε περισσότεραSupporting 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 περισσότεραSupplementary 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 περισσότεραIodine-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 περισσότεραSupporting Information for: Intramolecular Hydrogen Bonding-Assisted Cyclocondensation of. 1,2,3-Triazole Synthesis
Supporting Information for: Intramolecular Hydrogen Bonding-Assisted Cyclocondensation of α-diazoketones with Various Amines: A Strategy for Catalytic Wolff 1,2,3-Triazole Synthesis Zikun Wang, a Xihe
Διαβάστε περισσότεραSupporting Information
Supporting Information Wiley-VC 2009 69451 Weinheim, Germany S1 Supporting Information for: The Lowest Singlet and Triplet States of the Oxyallyl Diradical Takatoshi Ichino, Stephanie M. Villano, Adam
Διαβάστε περισσότεραElectronic 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 περισσότεραElectronic Supplementary Information (ESI)
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Electronic Supplementary Information (ESI) Cyclopentadienyl iron dicarbonyl (CpFe(CO) 2 ) derivatives
Διαβάστε περισσότεραRegioselectivity 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 περισσότεραEco-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 περισσότεραCycloaddition of Homochiral Dihydroimidazoles: A 1,3-Dipolar Cycloaddition Route to Optically Active Pyrrolo[1,2-a]imidazoles
X-Ray crystallographic data tables for paper: Supplementary Material (ESI) for Organic & Biomolecular Chemistry Cycloaddition of Homochiral Dihydroimidazoles: A 1,3-Dipolar Cycloaddition Route to Optically
Διαβάστε περισσότεραSupporting Information
Supporting Information Imidazol(in)ium Hydrogen Carbonates as a Genuine Source of N- Heterocyclic Carbenes (NHCs): Applications to the Facile Preparation of NHC Metal Complexes and to NHC- Organocatalyzed
Διαβάστε περισσότεραSUPPLEMENTARY MATERIAL. A Facile and Convenient Approach for the Synthesis of Novel Sesamol-Oxazine and Quinoline- Oxazine Hybrids
10.1071/CH17272_AC CSIRO 2017 Australian Journal of Chemistry 2017, 70(12), 1285-1290 SUPPLEMENTARY MATERIAL A Facile and Convenient Approach for the Synthesis of Novel Sesamol-Oxazine and Quinoline- Oxazine
Διαβάστε περισσότεραSupporting Information. A catalyst-free multicomponent domino sequence for the. diastereoselective synthesis of (E)-3-[2-arylcarbonyl-3-
Supporting Information for A catalyst-free multicomponent domino sequence for the diastereoselective synthesis of (E)-3-[2-arylcarbonyl-3- (arylamino)allyl]chromen-4-ones Pitchaimani Prasanna 1, Pethaiah
Διαβάστε περισσότεραSupplementary 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 περισσότεραEnantioselective Synthesis of the Anti-inflammatory Agent ( )-Acanthoic Acid
Enantioselective Synthesis of the Anti-inflammatory Agent ( )-Acanthoic Acid Taotao Ling, a Chinmay Chowdhury, a Bryan A. Kramer, a Binh G. Vong, a Michael A. Palladino b and Emmanuel A. Theodorakis a
Διαβάστε περισσότεραSupporting 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 περισσότεραSupporting 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 περισσότεραand 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 περισσότεραSupporting 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 περισσότεραVilsmeier 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 περισσότεραSupporting Information. Research Center for Marine Drugs, Department of Pharmacy, State Key Laboratory
Supporting Information Dysiherbols A C and Dysideanone E, Cytotoxic and NF-κB Inhibitory Tetracyclic Meroterpenes from a Dysidea sp. Marine Sponge Wei-Hua Jiao,, Guo-Hua Shi,, Ting-Ting Xu,, Guo-Dong Chen,
Διαβάστε περισσότεραSupporting 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 περισσότεραBis(perylene diimide) with DACH bridge as nonfullerene. electron acceptor for organic solar cells
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Supporting Information for Bis(perylene diimide) with DACH bridge as nonfullerene electron
Διαβάστε περισσότεραSupporting Information
Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2014 Bis- and Tris(pyrazolyl)borate/methane-Stabilized P III -Centered Cations Lianghu Gu, Gopinadhanpillai Gopakumar,
Διαβάστε περισσότεραSupporting 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 περισσότεραSupporting Information
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2017 Supporting Information Domino reaction of cyclic sulfamidate imines with
Διαβάστε περισσότεραSupporting 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 περισσότεραSupporting Information
Supporting Information for Solving the Density Functional Conundrum: Elimination of Systematic Errors to Derive Accurate Reaction Enthalpies of Complex rganic Reactions Arkajyoti Sengupta and Krishnan
Διαβάστε περισσότερα