One-pot Synthesis of 1-Alkyl-1H-indazoles. Supporting Information
|
|
- Ira Hood
- 5 years ago
- Views:
Transcription
1 One-pot Synthesis of 1-Alkyl-1H-indazoles from 1,1-Dialkylhydrazones via Aryne Annulation ataliya A. Markina, Anton V. Dubrovskiy, and Richard C. Larock* Department of Chemistry, Iowa State University, Ames, IA, 50011, USA Supporting Information Table of contents General procedure for the synthesis of,-dialkylhydrazones S2 Fluorohydrazone 7a S5 Characterization data for indazoles prepared via CS chlorination S6 General procedure for the preparation of 2-acetyl-1-methylindazolines S12 Characterization data for indazoles prepared via anion trap/deprotection S14 Procedure for the preparation of 1-benzyl-3-phenyl-1H-indazole S16 Copies of 1 H and 13 C MR spectra ( 19 F MR data for 7a ) S17-S80 OE data for compound 15l S81-S82 Copies of GC/MS spectra for crude 7a and 15a S83-84 S1
2 General procedure for the preparation of hydrazones 6 The starting hydrazones were prepared according to the procedure described in our recent communication. 1 The characterization of hydrazones 6a-6c, 6g, 6h, 6j-6m, 6p and 6r can be found therein. (E)-Methyl 4-[(2,2-dimethylhydrazono)methyl]benzoate 2 (6d) MeO 2 C Compound 6d was obtained as a colorless solid in a 96% yield: M. P C; 1 H MR (400 MHz, CDCl 3 ) δ 2.97 (s, 6H), 3.85 (s, 3H), 7.09 (s, 1H), 7.55 (d, J = 8.5 Hz, 2H), 7.94 (d, J = 8.5 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 42.55, 51.93, , , , , , ; MS (EI) m/z (%) 206 (M +, 97%), 163 (59%), 130 (100%), 102 (46%), 76 (23%), 44 (21%). IR (CH 2 Cl 2, cm -1 ) 2953 (w), 1716 (s), 1581 (m), 1550 (m). (E)-4-[(2,2-dimethylhydrazono)methyl]benzonitrile 2 (6e) C Compound 6e was obtained as a colorless solid in a 92% yield: M. P C; 1 H MR (300 MHz, CDCl 3 ) δ 3.04 (s, 6H), 7.05 (s, 1H), (m, 4H); 13 C MR (75 MHz, CDCl 3 ) δ 42.63, , , , , , MS (EI) m/z (%) 173 (M +, 100%), 158 (24%), 128 (67%), 42 (21%); IR (CH 2 Cl 2, cm -1 ) 2866 (w), 2223 (s), 1576 (s), 1545 (s), 1054 (s). 1 A. V. Dubrovskiy, R. C. Larock, Org. Lett. 2011, 13, M. Giurg, J. Mlochowski, A. Ambrozak, Polish J. Chem. 2002, 76, S2
3 4-Ethynylbenzaldehyde dimethylhydrazone (6f) Compound 6f was obtained as a light yellow solid in a 94% yield: M. P C; 1 H MR (300 MHz, CDCl 3 ) δ 3.00 (s, 6H), 3.10 (s, 1H), 7.16 (s, 1H), (m, 2H), (m, 2H); 13 C MR (75 MHz, CDCl 3 ) δ 42.90, 77.63, 84.26, , , , , ; MS (EI) m/z (%) 172 (M +, 100%); HRMS (ESI) calcd for [M+H] + C 11 H , found ; IR (CH 2 Cl 2, cm -1 ) 3295 (s), 2863 (w), 2105 (w), 1578 (s), 1546 (m), 1040 (s). Thiophene-2-carbaldehyde dimethylhydrazone 3 (6i) S Compound 6i was obtained as a green liquid in a 99% yield: 1 H MR (400 MHz, CDCl 3 ) δ 2.94 (s, 6H), (m, 2H), 7.13 (d, J = 4.9 Hz, 1H), 7.42 (s, 1H); 13 C MR (75 MHz, CDCl 3 ) δ 43.04, , , , , ; MS (EI) m/z (%) 154 (M +, 100%), 109 (27%); IR (neat, cm -1 ) 3084 (doublet, w), 2854 (m), 1570 (m), 1034 (m), 699 (m). (E)--Benzylidenepiperidin-1-amine 4 (6n) Compound 6n was obtained as a colorless solid in a 72% yield: M. P C; 1 H MR (400 MHz, CDCl 3 ) δ 1.57 (ddt, J = 11.7, 8.4, 4.8 Hz, 2H), 1.78 (p, J = 5.9 Hz, 4H), (m, 4H), 7.28 (t, J = 7.3 Hz, 1H), 7.37 (t, J = 7.6 Hz, 2H), 7.57 (s, 1H), (m, 2H); 13 C MR (75 MHz, CDCl 3 ) δ 24.12, 25.16, 51.99, , , , , 3 D. Perdicchia, E. Licandro, S. Maiorana, C. Baldoli, C. Giannini, Tetrahedron 2003, 59, H. Bohme, S. Ebel, Chem. Ber. 1965, 98, S3
4 136.74; MS (EI) m/z (%) 188 (M +, 100%), 131 (22%), 103 (26%), 77 (18%); IR (CH 2 Cl 2, cm -1 ) 2939 (m), 2856 (m), 1592 (m), 1565 (m), 1363 (m), 1087 (m), 992 (m). Dihydrocinnamaldehyde dimethylhydrazone 5 (6o) Compound 6o was obtained as a light yellow liquid in a 74% yield: 1 H MR (400 MHz, CDCl 3 ) δ 2.56 (q, J = 7.2, 6.6 Hz, 2H), 2.73 (s, 6H), 2.82 (t, J = 7.8 Hz, 2H), 6.67 (d, J = 5.5 Hz, 1H), 7.20 (dd, J = 12.4, 6.5 Hz, 3H), 7.29 (t, J = 7.5 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 34.31, 34.96, 43.51, , , , , ; MS (EI) m/z (%) 176 (M +, 15%), 91 (30%), 85 (100%), 44 (19%); IR (neat, cm -1 ) 3061 (w), 2952 (s), 2852 (s), 1603 (m), 1496 (s), 1029 (s), 699 (s). 2,4,6-Trimethoxybenzaldehyde dimethylhydrazone (6q) MeO OMe OMe Compound 6q was obtained as a light brown liquid in a 94% yield: 1 H MR (400 MHz, CDCl 3 ) δ 2.87 (s, 6H), 3.76 (s, 3H), 3.83 (d, J = 5.1 Hz, 6H), 6.42 (s, 1H), 7.37 (s, 1H), 7.53 (s, 1H); 13 C MR (100 MHz, CDCl 3 ) δ 43.11, 55.94, 56.15, 56.55, 97.34, , , , , , ; MS (EI) m/z (%) 238 (M +, 81%), 193 (93%), 179 (100%), 164 (25%), 151 (34%), 121 (23%), 44 (49%); HRMS (ESI) calcd for [M+H] + C 12 H 19 2 O , found ; IR (neat, cm -1 ) 3005 (w), 2941 (m), 2839 (m), 1676 (w), 1592 (s), 1468 (m), 1126 (s). 5 S. Denmark, J. P. Edwards, T. weber, D. W. Piotrowski, Tetrahedron Asymmetry 2010, 21, 1278 S4
5 (E)-Ethyl 2-(2,2-dimethylhydrazono)acetate 6 (6s) O EtO Compound 6s was obtained as a yellow liquid in a 69% yield: 1 H MR (400 MHz, CDCl 3 ) δ 1.28 (t, J = 7.1 Hz, 3H), 3.09 (s, 6H), 4.22 (q, J = 7.1 Hz, 2H), 6.35 (s, 1H); 13 C MR (75 MHz, CDCl 3 ) δ 14.42, 42.50, 60.15, , ; MS (EI) m/z (%) 144 (M +, 77%), 99 (34%), 71 (45%), 44 (100%); IR (neat, cm -1 ) 2981 (m), 1720 (s), 1545 (s), 1273 (s), 1184 (s), 1083 (s), 837 (m). Benzaldehyde dibenzylhydrazone 7 (6t) Compound 6t was obtained as a colorless solid in an 85% yield: M. P C; 1 H MR (400 MHz, CDCl 3 ) δ 4.57 (s, 4H), (m, 14H), 7.55 (d, J = 7.3 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 58.09, , , , , , , , , ; MS (EI) m/z (%) 300 (M +, 47%), 181 (14%), 166 (13%), 103 (15%), 91 (100%); IR (CH 2 Cl 2, cm -1 ) 3086 (w), 3029 (m), 2845 (w), 1589 (s), 1562 (s), 1494 (s), 1452 (s), 1129 (m). Data for the crude ','-dimethylbenzohydrazonoyl fluoride (7a ) F 6 T. Hoffman, Helv. Chim. Acta 1997, 80, P.. Anderson, J. T. Sharp, J. Chem. Soc. Perkin Trans , S5
6 1 H MR (400 MHz, CD 3 C) δ 2.83 (s, 6H), 7.44 (m, 3H), 7.73 (d, J = 7.9 Hz, 2H) (succinimide peak: δ 2.60); 19 F MR (400 MHz, CD 3 C) δ -66.6; MS (EI) m/z (%) 166 (M +, 100%), 103 (20%), 77 (19%), 42 (21%); HRMS (ESI) calcd for [M+H] + C 9 H 12 F , found Characterization data for indazoles 15 prepared via CS-chlorination. 1-Methyl-3-(naphthalen-2-yl)-1H-indazole (15b) H 3 C Product 15b was isolated as a yellow oil in a 76% yield: 1 H MR (400 MHz, CDCl 3 ) δ 4.19 (s, 3H), 7.27 (ddd, J = 7.7, 5.2, 2.0 Hz, 1H), 7.46 (d, J = 5.2 Hz, 2H), 7.53 (td, J = 5.2, 4.6, 2.1 Hz, 2H), 7.90 (d, J = 8.6 Hz, 1H), 7.98 (t, J = 7.9 Hz, 2H), 8.17 (d, J = 8.4 Hz, 2H), 8.44 (s, 1H); 13 C MR (100 MHz, CDCl 3 ) δ 35.81, , , , , , , , , , , , , , , , ; MS (EI) m/z (%) 258 (M +, 100%); HRMS (EI) calcd for [M+H] + C 15 H 15 2 O , found ; IR (CH 2 Cl 2, cm -1 ) 2937 (m), 1615 (s), 1494 (m). 3-(4-Methoxyphenyl)-1-methyl-1H-indazole (15c) H 3 C OCH 3 Product 15c was isolated as a yellow oil in a 72% yield: 1 H MR (400 MHz, CDCl 3 ) δ 3.88 (s, 3H), 4.11 (s, 3H), 7.05 (dd, J = 9.0, 2.2 Hz, 2H), 7.20 (ddd, J = 7.9, 5.5, 2.3 Hz, 1H), 7.41 (d, J = 5.4 Hz, 2H), 7.90 (dd, J = 9.0, 2.2 Hz, 2H), 7.99 (d, J = 8.2 Hz, 1H); 13 C S6
7 MR (100 MHz, CDCl 3 ) δ 35.66, 55.53, , , , , , , , , , , ; MS (EI) m/z (%) 238 (M +, 100%), 223 (61%), 195 (22%); HRMS (EI) calcd for [M+H] + C 15 H 15 2 O , found ; IR (CH 2 Cl 2, cm -1 ) 3007 (w), 2938 (m), 2838 (m), 1614 (s), 1530 (s), 1035 (s). Methyl 4-(1-methyl-1H-indazol-3-yl)benzoate (15d) H 3 C CO 2 Me Product 15d was isolated as a yellow solid in a 59% yield: M. P C; 1 H MR (400 MHz, CDCl 3 ) δ 3.95 (s, 3H), 4.14 (s, 3H), 7.25 (dt, J = 8.1, 4.2 Hz, 1H), 7.44 (d, J = 3.5 Hz, 2H), 8.04 (dd, J = 11.3, 8.5 Hz, 3H), 8.16 (d, J = 8.5 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 35.91, 52.34, , , , , , , , , , , , ; MS (EI) m/z (%) 266 (M +, 100%), 235 (61%), 208 (12%), 192 (13%); HRMS (EI) calcd for [M+H] + C 16 H 15 2 O , found ; IR (CH 2 Cl 2, cm -1 ) 2951 (m), 1720 (s), 1611 (s), 1114 (s). 4-(1-Methyl-1H-indazol-3-yl)benzonitrile (15e) H 3 C C Product 15e was isolated as a light yellow solid in a 45% yield: M. P C; 1 H MR (400 MHz, CDCl 3 ) δ 4.15 (s, 3H), (m, 1H), 7.46 (d, J = 3.6 Hz, 2H), (m, 2H), 7.99 (d, J = 8.3 Hz, 1H), 8.09 (d, J = 8.5 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 36.02, , , , , , , , , , S7
8 132.96, , , (the latter peak possibly appears due to the conformational restriction at the C-3 carbon of the indazole); MS (EI) m/z (%) 233 (M +, 100%); HRMS (EI) calcd for [M+H] + C 15 H , found ; IR (CH 2 Cl 2, cm -1 ) 2941 (w), 2228 (s), 1610 (s). 3-(4-Ethynylphenyl)-1-methyl-1H-indazole (15f) H 3 C Product 15f was isolated as a yellow solid in a 67% yield: M. P C; 1 H MR (400 MHz, CDCl 3 ) δ 3.16 (s, 1H), 4.13 (s, 3H), (m, 1H), 7.43 (s, 2H), 7.63 (d, J = 8.2 Hz, 2H), 7.95 (d, J = 8.2 Hz, 2H), 8.00 (d, J = 8.2 Hz, 1H); 13 C MR (100 MHz, CDCl 3 ) δ 35.84, 78.04, 83.91, , , , , , , , , , , ; MS (EI) m/z (%) 232 (M +, 100%); HRMS (EI) calcd for [M+H] + C 16 H , found ; IR (CH 2 Cl 2, cm -1 ) 3296 (s), 2940 (w), 2107 (w), 1615 (m), 1493 (m). 3-(2-Bromophenyl)-1-methyl-1H-indazole (15g) H 3 C Br Product 15g was isolated as a yellow oil in a 65% yield: 1 H MR (400 MHz, CDCl 3 ) δ 4.15 (s, 3H), 7.18 (ddd, J = 7.8, 5.6, 2.1 Hz, 1H), 7.30 (td, J = 7.7, 1.7 Hz, 1H), (m, 3H), 7.55 (dd, J = 7.6, 1.7 Hz, 1H), 7.68 (d, J = 8.2 Hz, 1H), (m, 1H); 13 C MR (100 MHz, CDCl 3 ) δ 35.86, , , , , , , , , , , , , ; MS (EI) m/z (%) 288 ([M+2] +, 90%), 286 S8
9 (M +, 100%), 206 (15%); HRMS (EI) calcd for [M+H] + C 14 H 12 Br , found ; IR (CH 2 Cl 2, cm -1 ) 2939 (m), 1617 (m), 1495 (m), 1027 (m). (E)-1-Methyl-3-styryl-1H-indazole (15h) H 3 C Ph Product 15h was isolated as a light brown solid in a 32% yield: M. P C; 1 H MR (400 MHz, CDCl 3 ) δ 4.09 (s, 3H), 7.24 (s, 2H), 7.40 (dd, J = 9.5, 6.6 Hz, 3H), (m, 2H), 7.60 (d, J = 7.4 Hz, 2H), 8.02 (d, J = 8.2 Hz, 1H); 13 C MR (100 MHz, CDCl 3 ) δ 35.76, , , , , , , , , , , , , ; MS (EI) m/z (%) 234 (M +, 90%), 233 ([M-H] +, 100%), 218 (48%); HRMS (EI) calcd for [M+H] + C 16 H , found ; IR (CH 2 Cl 2, cm -1 ) 3082 (w), 2937 (m), 1614 (m), 1493 (m), 962 (s). 1-Methyl-3-(thiophen-2-yl)-1H-indazole (15i) H 3 C S Product 15i was isolated as a yellow-green oil in a 60% yield: 1 H MR (300 MHz, CDCl 3 ) δ 4.10 (s, 3H), 7.17 (dd, J = 4.9, 3.7 Hz, 2H), (m, 2H), (m, 2H), (m, 3H), 7.63 (d, J = 3.6 Hz, 1H), 8.03 (d, J = 8.2 Hz, 1H); 13 C MR (75 MHz, CDCl 3 ) δ 35.75, , , , , , , , , , ; MS (EI) m/z (%) 214 (M +, 100%), 199 (25%); HRMS (EI) calcd for [M+H] + C 12 H 11 2 S , found ; IR (CH 2 Cl 2, cm -1 ) 3397 (m), 2948 (m), 2842 (m), 2798 (m), 1595 (m), 1494 (m). S9
10 1-Methyl-3-phenyl-1H-benzo[f]indazole (15j) H 3 C Product 15j was isolated as a yellow solid in a 63% yield: M. P C; 1 H MR (400 MHz, CDCl 3 ) δ 4.20 (s, 3H), (m, 1H), 7.46 (q, J = 6.6 Hz, 2H), 7.58 (t, J = 7.6 Hz, 2H), 7.78 (s, 1H), 7.94 (d, J = 8.5 Hz, 1H), 7.99 (d, J = 8.5 Hz, 1H), 8.10 (d, J = 7.3 Hz, 2H), 8.57 (s, 1H); 13 C MR (100 MHz, CDCl 3 ) δ 35.87, , , , , , , , , , , , , , ; MS (EI) m/z (%) 258 (M +, 100%); HRMS (EI) calcd for [M+H] + C 18 H , found ,6-Dimethoxy-1-methyl-3-phenyl-1H-indazole (15k) H 3 C MeO MeO Product 15k was isolated as a yellow solid in a 62% yield: M. P C; 1 H MR (400 MHz, CDCl 3 ) δ 3.95 (s, 3H), 3.99 (s, 3H), 4.06 (s, 3H), 6.74 (s, 1H), 7.28 (s, 1H), 7.37 (t, J = 7.8 Hz, 1H), 7.49 (t, J = 7.6 Hz, 2H), 7.89 (d, J = 7.3 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 35.84, 56.25, 56.46, 90.65, , , , , , , , , , ; MS (EI) m/z (%) 268 (M +, 100%), 253 (62%), 210 (17%);HRMS (EI) calcd for [M+H] + C 16 H 17 2 O , found ; IR (CH 2 Cl 2, cm -1 ) 3008 (w), 2937 (m), 2832 (m), 1713 (s), 1630 (s), 1206 (s). S10
11 4-Methoxy-1-methyl-3-phenyl-1H-indazole (15l) H 3 C OCH 3 Product 15l was isolated as a yellow solid in a 64% yield: M. P C; 1 H MR (400 MHz, CDCl 3 ) δ 3.90 (s, 3H), 4.09 (s, 3H), 6.52 (d, J = 7.7 Hz, 1H), 6.99 (d, J = 8.4 Hz, 1H), (m, 2H), 7.45 (t, J = 7.4 Hz, 2H), 7.93 (d, J = 8.4 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 35.86, 55.39, 99.92, , , , , , , , , , ; MS (EI) m/z (%) 238 (M +, 100%), 223 (18%), 208 (20%);HRMS (EI) calcd for [M+H] + C 15 H 15 2 O , found ; IR (CH 2 Cl 2, cm -1 ) 2937 (m), 2840 (w), 1614 (s), 1584 (s), 1507 (s), 1358 (s), 1182 (m). 1-[2-(2-(3-Phenyl-1H-indazol-1-yl)ethoxy)ethyl]pyrrolidine-2,5-dione (15m) O O O Ph Product 15m was isolated as a colorless oil in a 60% yield: 1 H MR (300 MHz, CDCl 3 ) δ 2.39 (s, 4H), (m, 2H), (m, 2H), 3.95 (t, J = 5.2 Hz, 2H), 4.56 (t, J = 5.3 Hz, 2H), (m, 1H), (m, 2H), (m, 3H), 7.95 (d, J = 8.0 Hz, 2H), 7.99 (d, J = 8.8 Hz, 1H); 13 C MR (75 MHz, CDCl 3 ) δ 28.09, 38.19, 49.22, 67.23, 69.82, , , , , , , , , , , , ; MS (EI) m/z (%) 363 (M +, 30%), 220 (28%), 207 (100%), 194 (32%), 77 (16%); HRMS (EI) calcd for [M+H] + C 21 H 22 3 O , found ; IR (CH 2 Cl 2, cm -1 ) 2944 (m), 2873 (m), 2798 (m), 1776 (m), 1704 (s), 1399 (m), 1123 (s). S11
12 1-[5-(3-Phenyl-1H-indazol-1-yl)pentyl]pyrrolidine-2,5-dione (15n) O O Ph Product 15n was isolated as an orange oil in a 60% yield: 1 H MR (400 MHz, CDCl 3 ) δ 1.35 (m, 2H), 1.62 (m, 2H), 1.99 (m, 2H), 2.62 (s, 4H), 3.48 (t, J = 7.3 Hz, 2H), 4.42 (t, J = 7.1 Hz, 2H), 7.20 (t, J = 7.0 Hz, 1H), 7.39 (dd, J = 14.4, 6.7 Hz, 3H), 7.50 (t, J = 7.6 Hz, 2H), 7.96 (d, J = 7.6 Hz, 2H), 8.01 (d, J = 8.2 Hz, 1H); 13 C MR (100 MHz, CDCl 3 ) δ 24.27, 27.41, 28.28, 29.55, 38.66, 48.75, , , , , , , , , , , , ; MS (EI) m/z (%) 361 (M +, 100%), 249 (53%), 194 (48%), 77 (29%); HRMS (EI) calcd for [M+H] + C 22 H 24 3 O , found ; IR (CH 2 Cl 2, cm -1 ) 2937 (m), 2862 (m), 1773 (m), 1693 (s), 1491 (s), 1351 (s). General procedure for the preparation of 2-acetyl-1-methylindazoles 17 [1-(1-Methyl-3-phenyl-1H-indazol-2(3H)-yl)ethanone (17a) as an example]. O To a mixture of benzaldehyde dimethylhydrazone 6a (37 mg, 0.25 mmol), CsF (114 mg, 0.75 mmol, 3 equiv), acetic anhydride (51 mg, 0.50 mmol, 2 equiv) and 5 ml of acetonitrile in a 10 ml vial, o-(trimethylsilyl)phenyl triflate (84 mg, 0.28 mmol, 1.1 equiv) was added. The vial was capped and the reaction mixture was allowed to stir for 10 h at 65 C. Then the reaction mixture was poured into 25 ml of water in a separatory funnel. After shaking the layers, the organic fraction was separated and the aqueous layer was extracted with dichloromethane (2 10 ml). All organic fractions were combined and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel S12
13 using hexanes/etoac as the eluent to afford the -acetylated product 17a. Product 17a was isolated as a light brown amorphous solid in an 83% yield as an inseparable mixture of diastereomers (ratio ~5:1): major diastereomer 1 H MR (400 MHz, CDCl3) δ 2.30 (s, 3H), 3.05 (s, 3H), 6.45 (s, 1H), 7.00 (d, J = 7.9 Hz, 1H), 7.10 (t, J = 7.4 Hz, 1H), (m, 2H), 7.31 (t, J = 6.5 Hz, 3H), 7.37 (d, J = 6.9 Hz, 3H); minor diastereomer (selected peaks) 1 H MR (400 MHz, CDCl3) δ 1.96 (s, 0.67H), 3.36 (s, 0.61H) 6.06 (s, 0.19H) 6.94 (s, 0.5H); 13 C MR (100 MHz, CDCl 3 ) (all of the peaks listed for the mixture of diastereomers) δ 21.45, 22.85, 45.71, 48.55, 64.20, 64.23, 67.97, , , , , , , , , , , , , , , , ; MS (EI) m/z (%) 252 (M +, 14%), 209 (100%), 194 (15%); HRMS (EI) calcd for [M+H] + C 16 H 17 2 O , found ; IR (CH 2 Cl 2, cm -1 ) 2921 (m), 1666 (s), 1610 (m), 1483 (m), 1381 (s). 1-[1-Methyl-3-phenethyl-1H-indazol-2(3H)-yl]ethanone (17o) O Product 17o was isolated as a light yellow amorphous solid in a 95% yield: 1 H MR (400 MHz, CDCl 3 ) δ 2.03 (dd, J = 12.0, 6.5 Hz, 1H), (m, 1H), 2.29 (s, 3H), 2.75 (d, J = 14.6 Hz, 1H), 2.88 (td, J = 12.7, 6.1 Hz, 1H), 3.09 (s, 3H), 5.45 (t, J = 5.6 Hz, 1H), 6.94 (d, J = 7.9 Hz, 1H), 7.07 (t, J = 7.4 Hz, 1H), (m, 4H), 7.28 (t, J = 7.2 Hz, 3H); 13 C MR (100 MHz, CDCl 3 ) δ 21.44, 32.48, 41.10, 48.61, 61.70, , , , , , , , , , , ; MS (EI) m/z (%) 280 (M +, 14%), 237 (85%), 175 (24%), 145 (71%), 133 (100%), 104 (33%), 77 (22%); HRMS (EI) calcd for [M+H] + C 18 H 21 2 O , found ; IR (CH 2 Cl 2, cm -1 ) 2920 (w), 2863 (w), 1660 (s), 1610 (w), 1385 (s). S13
14 Characterization data for indazoles 15 obtained via methods A and B. 3-Mesityl-1-methyl-1H-indazole 1 (15p) Product 15p was isolated as a red amorphous solid in a 91% yield (method A): 1 H MR (400 MHz, CDCl 3 ) δ 2.08 (s, 6H), 2.38 (s, 3H), 4.15 (s, 3H), 7.00 (s, 2H), 7.12 (t, J = 7.2 Hz, 1H), (m, 3H); 13 C MR (100 MHz, CDCl 3 ) δ 20.56, 21.37, 35.65, , , , , , , , , , , ; MS (EI) m/z (%) 250 (M +, 73%), 249 ([M-H] +, 100%), 235 (13%), 219 (11%); HRMS (EI) calcd for [M+H] + C 17 H , found ; IR (CH 2 Cl 2, cm -1 ) 3004 (m), 2921 (s), 2858 (m), 1614 (s), 1492 (s), 1337 (s). 1-Methyl-3-(2,4,6-trimethoxyphenyl)-1H-indazole (15q) OMe MeO OMe Product 15q was isolated as a yellow solid in a 76% yield (method A): M. P C; 1 H MR (400 MHz, CDCl 3 ) δ 3.71 (s, 6H), 3.89 (s, 3H), 4.13 (s, 3H), 6.27 (s, 2H), 7.08 (t, J = 7.2 Hz, 1H), (m, 2H), 7.46 (d, J = 8.1 Hz, 1H); 13 C MR (100 MHz, CDCl 3 ) δ 35.70, 55.55, 56.08, 90.95, , , , , , , , , , ; MS (EI) m/z (%) 298 (M +, 100%), 297 ([M-H] +, 39%), 267 (16%); HRMS (EI) calcd for [M+H] + C 17 H 19 2 O , found ; IR (CH 2 Cl 2, cm -1 ) 3009 (w), 2940 (m), 2839 (m), 1615 (s), 1587 (s), 1337 (s), 1127 (s). S14
15 1-Methyl-3-(pyridin-3-yl)-1H-indazole (15r) Product 15r was isolated as an orange amorphous solid in a 29% yield (method A): 1 H MR (400 MHz, CDCl 3 ) δ 4.07 (s, 3H), 7.18 (dt, J = 8.1, 4.0 Hz, 1H), 7.34 (dd, J = 7.9, 4.9 Hz, 1H), 7.37 (d, J = 3.6 Hz, 2H), 7.91 (d, J = 8.2 Hz, 1H), 8.17 (dt, J = 7.9, 1.8 Hz, 1H), 8.55 (dd, J = 4.7, 1.3 Hz, 1H), 9.15 (s, 1H); 13 C MR (100 MHz, CDCl 3 ) δ 35.89, , , , , , , , , , , , ; MS (EI) m/z (%) 209 (M +, 100%), 208 ([M-H] +, 33%), 181 (10%); HRMS (ESI) calcd for [M+H] + C 13 H , found ; IR (CH 2 Cl 2, cm -1 ) 3392 (w, broad), 2939 (m), 1618 (s), 1496 (s), 1153 (s). (E)-Ethyl 2-(acetylimino)-2-[2-(dimethylamino)phenyl]acetate (20) O O O Product 20 was isolated as an orange amorphous solid in a 54% yield (method A): 1 H MR (400 MHz, CDCl 3 ) δ 1.23 (t, J = 7.1 Hz, 3H), 2.36 (s, 3H), 2.66 (s, 6H), 4.22 (q, J = 7.1 Hz, 2H), (m, 2H), 7.47 (t, J = 7.7 Hz, 1H), 7.56 (d, J = 7.7 Hz, 1H); 13 C MR (75 MHz, CDCl 3 ) δ 14.26, 25.12, 45.00, 62.08, , , , , , , , , ; MS (EI) m/z (%) 262 (M +, 11%), 203 (82%), 189 (29%), 175 (19%), 158 (84%), 147 (100%), 131 (31%), 43 (26%); HRMS (ESI) calcd for [M+H] + C 14 H 19 2 O , found ; IR (CH 2 Cl 2, cm -1 ) 2942 (m), 2867 (m), 2835 (m) (m), 1736 (s), 1708 (s), 1652 (s), 1595 (s), 1490 (s). S15
16 Procedure for the preparation of 1-benzyl-3-phenyl-1H-indazole 8 (15t). To a mixture of benzaldehyde dibenzylhydrazone 6t (75 mg, 0.25 mmol), CsF (151 mg, 1.00 mmol, 4 equiv), and 5 ml of acetonitrile in a 10 ml vial, o-(trimethylsilyl)phenyl triflate (149 mg, 0.50 mmol, 2.0 equiv) was added. The vial was capped and the reaction mixture was allowed to stir for 10 h at 65 C. Then the reaction mixture was poured into 25 ml of water in a separatory funnel. After shaking the layers, the organic fraction was separated and the aqueous layer was extracted with dichloromethane (2 10 ml). All organic fractions were combined and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel using hexanes/etoac as the eluent to afford 15t as a yellow amorphous solid in a 51% yield: 1 H MR (400 MHz, CDCl 3 ) δ 5.68 (s, 2H), (m, 6H), 7.37 (d, J = 4.1 Hz, 2H), 7.42 (t, J = 7.4 Hz, 1H), 7.53 (t, J = 7.6 Hz, 2H), 8.02 (d, J = 7.1 Hz, 2H), 8.05 (d, J = 8.2 Hz, 1H); 13 C MR (100 MHz, CDCl 3 ) δ 53.29, , , , , , , , , , , , , , , ; MS (EI) m/z (%) 284 (M +, 100%), 91 (79%); HRMS (ESI) calcd for [M+H] + C 20 H , found ; IR (CH 2 Cl 2, cm -1 ) 2927 (m), 2854 (w), 1614 (s), 1493 (s), 1350 (s). 8 V. Collot, P. Dallemagne, P. R. Bovy, S. Rault, Tetrahedron 1999, 55, S16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
p-toluenesulfonic Acid-Mediated 1,3-Dipolar Cycloaddition of
Supporting Information for: p-toluenesulfonic Acid-Mediated 1,3-Dipolar Cycloaddition of Nitroolefins with NaN 3 for Synthesis of 4-Aryl-NH-1,2,3-triazoles Xue-Jing Quan, Zhi-Hui Ren, Yao-Yu Wang, and
More informationSchwartz s reagent-mediated regiospecific synthesis of 2,3-disubstituted indoles from isatins
Electronic Supplementary Information (ESI) Schwartz s reagent-mediated regiospecific synthesis of 2,3-disubstituted indoles from isatins A. Ulikowski and B. Furman* Institute of Organic Chemistry, Polish
More informationCu-Catalyzed Direct C6-Arylation of Indoles
Cu-Catalyzed Direct C6-Arylation of Indoles (Supporting Information) Youqing Yang, Ruirui Li, Yue Zhao, Dongbing Zhao, and Zhuangzhi Shi*, State Key Laboratory of Coordination Chemistry, Collaborative
More informationCopper(II) Ionic Liquid Catalyzed Cyclization-Aromatization of. Hydrazones with Dimethyl Acetylenedicarboxylate: A Green Synthesis
Copper(II) Ionic Liquid Catalyzed Cyclization-Aromatization of Hydrazones with Dimethyl Acetylenedicarboxylate: A Green Synthesis of Fully Substituted Pyrazoles Shirin Safaei, Iraj Mohammadpoor-Baltork,*
More informationSupporting Materials. Experimental Section. internal standard TMS (0 ppm). The peak patterns are indicated as follows: s, singlet; d,
CuBr-Catalyzed Efficient Alkynylation of sp 3 C-H Bonds Adjacent to a itrogen Atom Zhiping Li and Chao-Jun Li* Department of Chemistry, McGill University, 801 Sherbrooke St. West, Montreal, Quebec H3A
More informationSupporting Information
Supporting Information Synthesis of N-Heteropolycyclic Compounds Including Quinazolinone Skeletons by Using Friedel-Crafts Alkylation Bu Keun Oh, Eun Bi Ko, Jin Wook Han* and Chang Ho Oh* Department of
More informationSupporting Information
Supporting Information De Novo Synthesis of Polysubstituted Naphthols and Furans Using Photoredox Neutral Coupling of Alkynes with 2-Bromo-1,3-Dicarbonyl Compounds Heng Jiang, Yuanzheng Cheng, Yan Zhang,*
More informationSupporting Information. An Efficient Synthesis of Optically Active Physostigmine from Tryptophan via Alkylative Cyclization
Supporting Information An Efficient Synthesis of Optically Active Physostigmine from Tryptophan via Alkylative Cyclization Michiaki, Kawahara, Atsushi Nishida, Masako Nakagawa* Faculty of Pharmaceutical
More informationSupporting Information
Supporting Information B(C 6 F 5 ) 3 -catalyzed Regioselective Deuteration of Electronrich Aromatic and Heteroaromatic compounds Wu Li, Ming-Ming Wang, Yuya Hu and Thomas Werner* Leibniz-Institute of Catalysis
More informationRegioective Halogenation of 2-Substituted-1,2,3-Triazole via sp 2 C-H Activation
Regioective Halogenation of 2-Substituted-1,2,3-Triazole via sp 2 C-H Activation Qingshan Tian, Xianmin Chen, Wei Liu, Zechao Wang, Suping Shi, Chunxiang Kuang,* Department of Chemistry, Tongji University,
More informationSupporting Information
Supporting Information Unconventional Passerini Reaction towards α-aminoxyamides Ajay L. Chandgude, Alexander Dömling* Department of Drug Design, University of Groningen, Antonius Deusinglaan 1, 9713 AV
More informationDivergent Construction of Pyrazoles via Michael Addition of N-Aryl Hydrazones to 1,2-Diaza-1,3-dienes
Divergent Construction of Pyrazoles via Michael Addition of N-Aryl Hydrazones to 1,2-Diaza-1,3-dienes Serena Mantenuto, Fabio Mantellini, Gianfranco Favi,* and Orazio A. Attanasi Department of Biomolecular
More informationCatalyst-free chemoselective N-tert-butyloxycarbonylation of amines in water
SUPPORTING INFORMATION Catalyst-free chemoselective N-tert-butyloxycarbonylation of amines in water Sunay V. Chankeshwara and Asit K. Chakraborti* National Institute of Pharmaceutical Education and Research
More informationSupplemental materials for:
Tambar and Stoltz, Supporting Information 1 Supplemental materials for: The Direct Acyl-Alkylation of Arynes Uttam K. Tambar and Brian M. Stoltz* The Arnold and Mabel Beckman Laboratories of Chemical Synthesis,
More informationPreparation of Fluorinated Tetrahydropyrans and Piperidines using a New Nucleophilic Fluorination Reagent DMPU/HF
Supporting information Preparation of Fluorinated Tetrahydropyrans and Piperidines using a New Nucleophilic Fluorination Reagent DMPU/HF Otome E. Okoromoba, a Gerald B. Hammond, a, * Bo Xu b, * a Department
More informationNHC-catalyzed cleavage of vicinal diketones and. triketones followed by insertion of enones and
Supporting Information for NHC-catalyzed cleavage of vicinal diketones and triketones followed by insertion of enones and ynones Ken Takaki*, Makoto Hino, Akira Ohno, Kimihiro Komeyama, Hiroto Yoshida
More informationLewis acid-catalyzed regioselective synthesis of chiral α-fluoroalkyl amines via asymmetric addition of silyl dienolates to fluorinated sulfinylimines
Supporting Information for Lewis acid-catalyzed regioselective synthesis of chiral α-fluoroalkyl amines via asymmetric addition of silyl dienolates to fluorinated sulfinylimines Yingle Liu a, Jiawang Liu
More informationSupporting Information
Palladium-Catalyzed Cascade Oxidantion/sp 2 C-H Acylation of Azoarenes with Aryl Methanes Feng Xiong, a Cheng Qian, b Dongen Lin, b Wei Zeng b,* and Xiaoxia Lu a,* a Chengdu Institute of Biology,CAS, Chengdu
More informationPyridazine N-Oxides as Precursors of Metallocarbenes: Rhodium-Catalyzed Transannulation with Pyrroles. Supporting Information
Pyridazine N-Oxides as Precursors of Metallocarbenes: Rhodium-Catalyzed Transannulation with Pyrroles Vinaykumar Kanchupalli, Desna Joseph and Sreenivas Katukojvala* Department of Chemistry, Indian Institute
More informationRameshwar Prasad Pandit and Yong Rok Lee * School of Chemical Engineering, Yeungnam University, Gyeongsan , Korea
Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2014 Novel ne-pot Synthesis of Diverse γ,δ-unsaturated β-ketoesters by Thermal
More informationSupporting Information. Copper-catalyzed cascade synthesis of benzimidazoquinazoline derivatives under mild condition
Supporting Information Copper-catalyzed cascade synthesis of benzimidazoquinazoline derivatives under mild condition Shan Xu, Juyou Lu and Hua Fu* Key Laboratory of Bioorganic Phosphorus Chemistry and
More informationSupporting Information. Efficient copper-catalyzed Michael addition of acrylic derivatives with primary alcohols in the presence of base
Supporting Information Efficient copper-catalyzed Michael addition of acrylic derivatives with primary alcohols in the presence of base Feng Wang, a Haijun Yang, b Hua Fu, b,c * and Zhichao Pei a * a College
More informationSupporting Information for. Use of the Curtius Rearrangement of Acryloyl Azides in the Synthesis of. 3,5-Disubstituted Pyridines: Mechanistic Studies
Supporting Information for Use of the Curtius Rearrangement of Acryloyl Azides in the Synthesis of 3,5-Disubstituted Pyridines: Mechanistic Studies Ta-Hsien Chuang* a, Yu-Chi Chen b and Someshwar Pola
More information1,5-Electrocyclization of conjugated azomethine ylides derived from 3-formyl chromene and N-alkyl amino acids/esters
Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 7 Supporting Information for,5-electrocyclization of conjugated azomethine ylides
More informationMasatoshi Shibuya,Takahisa Sato, Masaki Tomizawa, and Yoshiharu Iwabuchi* Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences,
Oxoammonium ion/naclo 2 : An Expedient, Catalytic System for One-pot Oxidation of Primary Alcohols to Carboxylic Acid with Broad Substrate Applicability Masatoshi Shibuya,Takahisa Sato, Masaki Tomizawa,
More informationSupporting Information. Palladium-Catalyzed Formylation of Aryl Iodides with HCOOH as
Supporting Information Palladium-Catalyzed Formylation of Aryl Iodides with HCOOH as CO Source Guanglong Sun,,, Xue Lv,,, Yinan Zhang, Min Lei,*,, and Lihong Hu*, Jiangsu Key Laboratory for Functional
More informationSynthesis and Blastocyst Implantation Inhibition Potential of Lupeol Derivatives in Female Mice
Supporting Information Rec. Nat. Prod. 9:4 (2015) 561-566 Synthesis and Blastocyst Implantation Inhibition Potential of Lupeol Derivatives in Female Mice Anita Mahapatra 1*, Purvi Shah 1, Mehul Jivrajani
More informationby Donor-Acceptor Complex
Metal-Free C(sp 3 )-H Allylation via Aryl Carboxyl Radicals Enabled by Donor-Acceptor Complex Yang Li 1+, Jing Zhang 1+, Defang Li 1,2, and Yiyun Chen 1,2 * Supplementary Information I. General Procedures...
More informationSupplementary Materials Contents
Supplementary Materials Contents Supporting information... S1 1. General Information & Materials... S2 2. General Procedure for ptimization of Amidation of Aryl Bromides with Copper/,-Dimethylglycine Catalytic
More informationSupporting information
Supporting information Diversity Oriented Asymmetric Catalysis (DOAC): Stereochemically Divergent Synthesis of Thiochromanes Using an Imidazoline-aminophenol aminophenol (IAP)-Ni Catalyzed Michael/Henry
More informationCDI Mediated Monoacylation of Symmetrical Diamines and Selective Acylation of Primary Amines of Unsymmetrical Diamines
Supporting information: CDI Mediated Monoacylation of Symmetrical Diamines and Selective Acylation of Primary Amines of Unsymmetrical Diamines Sanjeev K. Verma*, Ramarao Ghorpade, Ajay Pratap and M. P.
More informationElectronic Supplementary Information
Efficient aerobic oxidative synthesis of 2-aryl quinazolines via benzyl C-H bond amination catalyzed by 4-hydroxy-TEMPO Bing Han,* Chao Wang, Run-Feng Han, Wei Yu,* Xiao-Yong Duan, Ran Fang and Xiu-Long
More informationSupporting Information. Use of Potassium. -Trifluoroborato Amides in Suzuki-Miyaura. Cross-Coupling Reactions
Supporting Information Use of Potassium -Trifluoroborato Amides in Suzuki-Miyaura Cross-Coupling Reactions Gary A. Molander* and Ludivine Jean-Gérard Roy and Diana Vagelos Laboratories, Department of Chemistry,
More informationNational Defense Academy, Hashirimizu, Yokosuka, , Japan
Suppoing Information for Reaction of Arynes with Amino Acid Esters Kentaro kuma, a * ahoko Matsunaga, a oriyoshi agahora, a Kosei Shioji, a and Yoshinobu Yokomori b a Depament of Chemistry, Faculty of
More informationSUPPORTING INFORMATION FOR. Regioselective Ring-opening and Isomerization Reactions of 3,4-Epoxyesters Catalyzed by Boron Trifluoride
S1 SUPPORTING INFORMATION FOR Regioselective Ring-opening and Isomerization Reactions of 3,4-Epoxyesters Catalyzed by Boron Trifluoride Javier Izquierdo, Santiago Rodríguez and Florenci V. González* Departament
More informationSupporting Information
Electronic Supplementary Material (ESI) for rganic Chemistry Frontiers. This journal is the Partner rganisations 2016 Supporting Information Fangyi Li, Changgui Zhao, and Jian Wang* Department of Pharmacology
More informationSupporting Information for. Visible Light Mediated Intermolecular C H Functionalization of Electron Rich Heterocycles with Malonates
Supporting Information for Visible Light Mediated Intermolecular C H Functionalization of Electron Rich Heterocycles with Malonates Laura Furst, Bryan S. Matsuura, Jagan M.R. Narayanam, Joseph W. Tucker,
More informationSupporting Information
Supporting Information A Regioselective Ring-Expansion of Isatins with In-situ Generated α-aryldiazomethanes; Direct Access to Viridicatin Alkaloids Yellaiah Tangella,, Kesari Lakshmi Manasa,, Namballa
More informationSupporting Information Synthesis of 2-Aminobenzonitriles through Nitrosation Reaction and Sequential Iron(III)-Catalyzed C C Bond Cleavage of 2-Arylin
Supporting Information Synthesis of 2-Aminobenzonitriles through Nitrosation Reaction and Sequential Iron(III)-Catalyzed C C Bond Cleavage of 2-Arylindoles Wei-Li Chen, Si-Yi Wu, Xue-Ling Mo, Liu-Xu Wei,
More informationCopper-Catalyzed Cascade Cycloamination of alpha-csp 3 -H Bond of N-Aryl Ketimines with Azides: Access to Quinoxalines. Supporting Information
Copper-Catalyzed Cascade Cycloamination of alpha-csp 3 -H Bond of N-Aryl Ketimines with Azides: Access to Quinoxalines Tengfei Chen, Xun Chen, Jun Wei, Dongen Lin *, Ying Xie, and Wei Zeng * School of
More informationSupporting Information
Zinc-Mediated Addition of Diethyl Bromomalonate to Alkynes for the Cascade Reaction towards Polysubstituted Pyranones and Tetracarbonyl Derivatives Anne Miersch, Klaus Harms, and Gerhard Hilt* Fachbereich
More informationSupporting Information
Supporting Information Wiley-VCH 2010 69451 Weinheim, Germany Direct, One-pot Sequential Reductive Alkylation of Lactams/Amides with Grignard and Organolithium Reagents through Lactam/Amide Activation**
More informationSupplementary Material. Efficient Synthesis of an Indinavir Precursor from Biomass Derived (-)- Levoglucosenone
1.171/CH17227_AC CSIRO 217 Australian Journal of Chemistry 217, 7(1), 1146-115 Supplementary Material Efficient Synthesis of an Indinavir Precursor from Biomass Derived (-)- Levoglucosenone Edward T. Ledingham,
More informationSupporting Information for. Boronic Acid Functionalized Aza-Bodipy (azabdpba) based Fluorescence Optodes for the. analysis of Glucose in Whole Blood
Supporting Information for Boronic Acid Functionalized Aza-Bodipy (azabdpba) based Fluorescence Optodes for the analysis of Glucose in Whole Blood Yueling Liu, Jingwei Zhu, Yanmei Xu, Yu Qin*, Dechen Jiang*
More informationStereoselective Aza-Darzens Reactions of Tert- Butanesulfinimines: Convenient Access to Chiral Aziridines
Stereoselective Aza-Darzens Reactions of Tert- Butanesulfinimines: Convenient Access to Chiral Aziridines Toni Moragas Solá, a Ian Churcher, b William Lewis a and Robert A. Stockman* a Supplementary Information
More informationSupporting Information. for. Access to pyrrolo-pyridines by gold-catalyzed. hydroarylation of pyrroles tethered to terminal alkynes
Supporting Information for Access to pyrrolo-pyridines by gold-catalyzed hydroarylation of pyrroles tethered to terminal alkynes Elena Borsini 1, Gianluigi Broggini* 1, Andrea Fasana 1, Chiara Baldassarri
More informationAn Electrophilic Reagent for the Synthesis of OCHFMe-containing Molecules
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2018 An Electrophilic Reagent for the Synthesis of OCHFMe-containing Molecules Elodie Carbonnel, a Xavier
More informationPreparation of Stable Aziridinium Ions and Their Ring Openings
Supplementary Information Preparation of Stable Aziridinium Ions and Their Ring Openings Yongeun Kim a Hyun-Joon Ha*, a Sae Young Yun b and Won Koo Lee,*,b a Department of Chemistry and Protein Research
More informationRuthenium-Catalyzed C H Oxygenation on Aryl Weinreb Amides
Supporting Information Ruthenium-Catalyzed C H xygenation on Aryl Weinreb Amides Fanzhi Yang and Lutz Ackermann* Institut für rganische und Biomolekulare Chemie Georg-August-Universität Tammannstrasse
More informationSimple copper/tempo catalyzed aerobic dehydrogenation. of benzylic amines and anilines
Simple copper/tempo catalyzed aerobic dehydrogenation of benzylic amines and anilines Zhenzhong Hu and Francesca M. Kerton,* Department of Chemistry, Memorial University of Newfoundland, St. John s, NL,
More informationPalladium-Catalyzed Regioselective C-2 Arylation of 7-Azaindoles, Indoles, and Pyrroles with Arenes. Supporting Information
Electronic Supplementary Material (ESI) for Chemical Communications. This journal is The Royal Society of Chemistry 2016 Palladium-Catalyzed Regioselective C-2 Arylation of 7-Azaindoles, Indoles, and Pyrroles
More informationElectronic Supplementary Information. Quinine/Selectfluor Combination Induced Asymmetric Semipinacol Rearrangement of
Electronic Supplementary Information Quinine/Selectfluor Combination Induced Asymmetric Semipinacol Rearrangement of Allylic Alcohols: An Effective and Enantioselective Approach to α Quaternary β Fluoro
More informationBase-promoted acetal formation employing aryl salicylates
Base-promoted acetal formation employing aryl salicylates Pinmanee Boontheung, Patrick Perlmutter*, and Evaloni Puniani School of Chemistry, Monash University, PO Box 23, Victoria 3800 Australia E-mail:
More informationThree-component synthesis of α-branched amines under Barbier-like conditions
Three-component synthesis of α-branched amines under Barbier-like conditions Erwan Le Gall*, Caroline Haurena, Stéphane Sengmany, Thierry Martens and Michel Troupel Électrochimie et Synthèse Organique,
More informationDirect Aerobic Carbonylation of C(sp 2 )-H and C(sp 3 )-H Bonds through Ni/Cu Synergistic Catalysis with DMF as the Carbonyl Source
Direct Aerobic Carbonylation of C(sp 2 )-H and C(sp 3 )-H Bonds through Ni/Cu Synergistic Catalysis with DMF as the Carbonyl Source Xuesong Wu, Yan Zhao, and Haibo Ge* Table of Contents General Information...
More informationDirect ortho-c H Functionalization of Aromatic Alcohols Masked by Acetone Oxime Ether via exo-palladacycle
Direct ortho-c H Functionalization of Aromatic Alcohols Masked by Acetone Oxime Ether via exo-palladacycle Kun Guo, Xiaolan Chen, Mingyu Guan, and Yingsheng Zhao* Key Laboratory of Organic Synthesis of
More informationEXPERIMENTAL PROCEDURES, OPTIMIZATION STUDIES, CHARACTERIZATION DATA and NMR SPECTRA
Supporting Information for Chemical Communications: S1 SUPPRTING INFRMATIN FR CHEM. CMMUN. Direct, facile synthesis of N-acyl-α-amino amides from α-keto esters and ammonia Rukundo Ntaganda, a Tamara Milovic,
More informationElectronic Supplementary Information (ESI)
Electronic Supplementary Information (ESI) Mild and convenient one-pot synthesis of 2-amino-1,3,4-oxadiazoles promoted by trimethylsilyl isothiocyanate (TMSNCS) Dinneswara Reddy Guda, Hyeon Mo Cho, Myong
More information# Supplementary Material (ESI) for Chemical Communications # This journal is The Royal Society of Chemistry 2005
Electronic Supplementary Information for: (Z)-Selective cross-dimerization of arylacetylenes with silylacetylenes catalyzed by vinylideneruthenium complexes Hiroyuki Katayama,* Hiroshi Yari, Masaki Tanaka,
More informationSUPPLEMENTARY INFORMATION
doi:10.1038/nature14875 Switching on Elusive rganometallic chanisms with Photoredox Catalysis Jack A. Terrett, James D. Cuthbertson, Valerie W. Shurtleff, and David W. C. MacMillan WWW.NATURE.CM/NATURE
More informationPalladium(II)-Catalyzed Cross-Coupling of Simple Alkenes with Acrylates: A Direct Approach to 1,3-Dienes through C H Activation
1 Palladium(II)-Catalyzed Cross-Coupling of Simple Alkenes with Acrylates: A Direct Approach to 1,3-Dienes through C H Activation Zhen-Kang Wen, Yun-He Xu* and Teck-Peng Loh* Division of Chemistry and
More informationManganese powder promoted highly efficient and selective synthesis of fullerene mono- and biscycloadducts at room temperature
Supplementary Information Manganese powder promoted highly efficient and selective synthesis of fullerene mono- and biscycloadducts at room temperature Weili Si 1, Xuan Zhang 1, Shirong Lu 1, Takeshi Yasuda
More informationSupporting Information
Supporting Information Cobalt-Catalyzed Carbonylation of C(sp 2 )-H Bonds with Azodicarboxylate as the Carbonyl Source Jiabin Ni,, Jie Li,,š Zhoulong Fan,, and Ao Zhang *,,,š CAS Key Laboratory of Receptor
More informationCatalytic decarboxylative alkylation of β-keto acids with sulfonamides via the cleavage of carbon nitrogen and carbon carbon bonds
Catalytic decarboxylative alkylation of β-keto acids with sulfonamides via the cleavage of carbon nitrogen and carbon carbon bonds Cui-Feng Yang, Jian-Yong Wang and Shi-Kai Tian* Joint Laboratory of Green
More informationIron-Catalyzed Alkylation of Alkenyl Grignard Reagents
Supporting Information for Iron-Catalyzed Alkylation of Alkenyl Grignard Reagents Gérard Cahiez,* Christophe Duplais and Alban Moyeux Laboratoire de Synthèse Organique Sélective et de Chimie Organométallique
More informationEfficient Metal-Free Pathway to Vinyl Thioesters with Calcium Carbide as the Acetylene Source
Electronic Supplementary Material (ESI) for Green Chemistry. This journal is The Royal Society of Chemistry 2015 Supporting Information Efficient Metal-Free Pathway to Vinyl Thioesters with Calcium Carbide
More informationZinc Chloride Promoted Formal Oxidative Coupling of Aromatic Aldehydes and Isocyanides to α- Ketoamides
Supporting information for Zinc Chloride Promoted Formal xidative Coupling of Aromatic Aldehydes and Isocyanides to α- Ketoamides Marinus Bouma, Géraldine Masson* and Jieping Zhu* Institut de Chimie des
More informationA General and Efficient 2-Amination of Pyridines and Quinolines
A General and Efficient 2-Amination of Pyridines and Quinolines Jingjun Yin,* Bangping Xiang,* Mark A. Huffman, Conrad E. Raab, and Ian W. Davies Department of Process Research, rck Research Laboratories,
More informationSupporting information for. Synthesis of phenothiazines from cyclohexanones and. 2-aminobenzenethiols under transition-metal-free conditions
Supporting information for Synthesis of phenothiazines from cyclohexanones and 2-aminobenzenethiols under transition-metal-free conditions Yunfeng Liao, a Pengcheng Jiang, a Shanping Chen, a Fuhong Xiao,
More informationSupporting Information
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2011 Supporting Information Potassium tert-butoxide Mediated Heck-Type Cyclization/Isomerization
More informationSupplementary Information. Intramolecular 5-exo, 7-endo-dig Transition Metal-Free Cyclization
Electronic Supplementary Material (ESI) for Green Chemistry. This journal is The Royal Society of Chemistry Supplementary Information Intramolecular -exo, -endo-dig Transition Metal-Free Cyclization Sequence
More informationSupplementary Information
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2018 Supplementary Information Oxidative Tandem Annulation of 1 (2 Ethynylaryl)prop 2 en 1 ones Catalyzed
More informationSUPPORTING INFORMATION
SUPPORTING INFORMATION Synthesis and Preliminary Pharmacological Evaluation of Aryl Dithiolethiones with Cyclooxygenase-2 Selective Inhibitory Activity and Hydrogen-Sulfide-Releasing Properties Shannon
More informationYnamides as racemization-free coupling reagents for amide and peptide synthesis
Ynamides as racemization-free coupling reagents for amide and peptide synthesis Long Hu, Silin Xu, Zhenguang Zhao, Yang Yang, Zhiyuan Peng, Ming Yang, Changliu Wang, Junfeng Zhao* Key Laboratory of Chemical
More informationPalladium-Catalyzed Oxidative Amination on Alkenes: Improved Catalyst Reoxidation Enables the Use of Alkene as the Limiting Reagent
S1 Supporting Information for Palladium-Catalyzed xidative Amination on Alkenes: Improved Catalyst Reoxidation Enables the Use of Alkene as the Limiting Reagent Michelle M. Rogers, Vasily Kotov, Jaruwan
More informationEnantioselective synthesis of anti- and syn-β-hydroxy-α-phenyl carboxylates via boron-mediated asymmetric aldol reaction
Enantioselective synthesis of anti- and syn-β-hydroxy-α-phenyl carboxylates via boron-mediated asymmetric aldol reaction P. Veeraraghavan Ramachandran* and Prem B. Chanda Department of Chemistry, Purdue
More informationSupporting Information. Total Synthesis of Grandisine D. Haruaki Kurasaki, Iwao Okamoto, Nobuyoshi Morita, and Osamu Tamura*
Supporting Information Total Synthesis of Grandisine D Haruaki Kurasaki, Iwao Okamoto, Nobuyoshi Morita, and Osamu Tamura* Discovery Research Laboratories, Kyorin Pharmaceutical Co. Ltd. 2399-1, Nogi,
More informationDepartment of Chemistry, Colorado State University, Fort Collins, CO 80523, USA. These authors contributed equally
Supporting Information Asymmetric δ-lactam Synthesis with a Monomeric Streptavidin Artificial Metalloenzyme Isra S. Hassan 1, Angeline N. Ta 2, Michael W. Danneman 1,2, Natthawat Semakul 1,2, Matthew Burns
More informationDirected Ortho Lithiation of N-Alkylphenylaziridines
Directed rtho Lithiation of -Alkylphenylaziridines Vito Capriati, Saverio Florio,* Renzo Luisi, Biagia Musio Dipartimento Farmaco-Chimico, Università di Bari, Via E. rabona 4, I-70126 Bari, C..R., Istituto
More informationChristophe Lincheneau, Bernard Jean-Denis and Thorfinnur Gunnlaugsson* Electronic Supplementary Information
Self-assembly formation of mechanically interlocked [2]- and [3]catenanes using lanthanide ion [Eu(III)] templation and ring closing metathesis reactions Christophe Lincheneau, Bernard Jean-Denis and Thorfinnur
More informationSupporting Information. as the nitro source
Supporting Information Efficient ipso-nitration of arylboronic acids with iron nitrate as the nitro source Min Jiang, a,b Haijun Yang,* a,b Yong Li, a,b Zhiying Jia b and Hua Fu b a Beijing Key Laboratory
More informationEur. J. Org. Chem WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007 ISSN X SUPPORTING INFORMATION
Eur. J. Org. Chem. 2007 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2007 ISSN 1434 193X SUPPORTING INFORMATION Title: Effect of Varying the Anionic Component of a Copper(I) Catalyst on Homologation
More informationHighly efficient hydrazination of conjugated nitroalkenes via imidazole or DMAP mediated Morita-Baylis-Hillman reaction
Experimental Data and ptimization Tables For Highly efficient hydrazination of conjugated nitroalkenes via imidazole or DMAP mediated Morita-Baylis-Hillman reaction M. Dadwal, S. M. Mobin, I... amboothiri
More informationChemo- and Enantioselective Rh-Catalyzed Hydrogenation of 3-Methylene-1,2-diazetidines: Application to Vicinal Diamine Synthesis
Chemo- and Enantioselective Rh-Catalyzed Hydrogenation of 3-Methylene-1,2-diazetidines: Application to Vicinal Diamine Synthesis Greg P. Iacobini, a David W. Porter, b and Michael Shipman* a a Department
More informationSupplemental Material
Supplemental Material General Methods Unless otherwise indicated, all anhydrous solvents were commercially obtained and stored under nitrogen. Reactions were performed under an atmosphere of dry nitrogen
More informationAllenylphosphine oxides as simple scaffolds for. phosphinoylindoles and phosphinoylisocoumarins
Supporting Information for Allenylphosphine oxides as simple scaffolds for phosphinoylindoles and phosphinoylisocoumarins G. Gangadhararao, Ramesh Kotikalapudi, M. Nagarjuna Reddy and K. C. Kumara Swamy*
More informationNovel Aldosterone Synthase Inhibitors with Extended Carbocyclic Skeleton by a Combined Ligand-Based and Structure-Based Drug Design Approach
Supporting Information Novel Aldosterone Synthase Inhibitors with Extended Carbocyclic Skeleton by a Combined Ligand-Based and Structure-Based Drug Design Approach Simon Lucas, Ralf Heim, Matthias Negri,
More informationSupplementary Information
Electronic Supplementary Material (ESI) for Green Chemistry. This journal is The Royal Society of Chemistry 2014 Supplementary Information A highly efficient approach to vanillin starting from 4-cresol
More informationChiral Squaramide Derivatives are Excellent Hydrogen Bond Donor Catalysts. Jeremiah P. Malerich, Koji Hagihara, and Viresh H.
Chiral Squaramide Derivatives are Excellent ydrogen Bond Donor Catalysts Jeremiah P. Malerich, Koji agihara, and Viresh. Rawal* Department of Chemistry, University of Chicago, Chicago, Illinois 60637 E-mail:
More informationSupporting Information
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2018 Supporting Information Facile Three-Step Synthesis and Photophysical Properties of [8]-, [9]-,
More informationph Switchable and Fluorescent Ratiometric Squarylium Indocyanine Dyes as Extremely Alkaline Sensors
ph Switchable and Fluorescent Ratiometric Squarylium Indocyanine Dyes as Extremely Alkaline Sensors Jie Li, Chendong Ji, Wantai Yang, Meizhen Yin* State Key Laboratory of Chemical Resource Engineering,
More informationSupporting Information
Supporting Information Accessing 1,3-Dienes via Palladium-Catalyzed Allylic Alkylation of Pronucleophiles with Skipped Enynes Shang Gao, + Hao Liu, + Chi Yang, Zhiyuan Fu, Hequan Yao* and Aijun Lin* State
More informationNaoya Takahashi, Keiya Hirota and Yoshitaka Saga* Supplementary material
Supplementary material Facile transformation of the five-membered exocyclic E-ring in 13 2 -demethoxycarbonyl chlorophyll derivatives by molecular oxygen with titanium oxide in the dark Naoya Takahashi,
More informationSupporting Information. Palladium-catalyzed reductive cleavage of tosylated arene using isopropanol as the mild reducing agent
Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers. This journal is the Partner Organisations 2014 Supporting Information Supporting Information Palladium-catalyzed reductive cleavage
More informationTransition Metal Free Intramolecular Selective Oxidative C(sp 3 )-N Coupling: Synthesis of N-Arylisoindolinones
Electronic Supplementary Material (ESI) for Chemical Communications. This journal is The Royal Society of Chemistry 2014 Supporting information for Transition Metal Free Intramolecular Selective xidative
More informationSupporting Information
Supporting Information Enantioselective Phosphine-Catalyzed Allylic Alkylations of mix- Indene with MBH Carbonates Junyou Zhang, Hai-Hong Wu,* and Junliang Zhang* Shanghai Key Laboratory of Green Chemistry
More informationSelf-organization of dipyridylcalix[4]pyrrole into a supramolecular cage for dicarboxylates
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Electronic Supplementary Information Self-organization of dipyridylcalix[4]pyrrole into a supramolecular
More informationUse of degradable cationic surfactants with cleavable linkages for enhancing the. chemiluminescence of acridinium ester labels. Supplementary Material
Use of degradable cationic surfactants with cleavable linkages for enhancing the chemiluminescence of acridinium ester labels Supplementary Material Anand atrajan*and David Wen Siemens Healthcare Diagnostics
More informationSUPPORTING INFORMATION
SUPPORTING INFORMATION Identification of the best-suited leaving group for the diastereoselective synthesis of glycidic amides from stabilised ammonium ylides and aldehydes Richard Herchl, a Martin Stiftinger,
More informationA Hierarchy of Aryloxide Deprotection by Boron Tribromide. Supporting Information
A Hierarchy of Aryloxide Deprotection by Boron Tribromide Sreenivas Punna, Stéphane Meunier and M. G. Finn* Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute,
More information