Synthesis of 3,4-diarylbenzophenones by site-selective suzuki-miyaura reactions of 3,4-Bis(trifluoromethylsulfonyloxy)benzophenone

Synlett

Volumn , Issue 6, 2010, Pages 979-981

  Nawaz, Muhammad ^a   Khera, Rasheed Ahmad ^a   Malik, Imran ^a   Ibad, Muhammad Farooq ^a   Abid, Obaid Ur Rahman ^a   Villinger, Alexander ^a   Langer, Peter ^a  

^a UNIVERSITY OF ROSTOCK   (Germany)

Author keywords

Benzophenones; Catalysis; Palladium; Site selectivity; Suzuki Miyaura reaction

Indexed keywords

3,4 BIS(TRIFLUOROMETHYLSULFONYLOXY)BENZOPHENONE; 3,4 DIARYLBENZOPHENONE DERIVATIVE; BENZOPHENONE DERIVATIVE; BORONIC ACID DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; DRUG SELECTIVITY; DRUG STRUCTURE; DRUG SYNTHESIS; SUZUKI REACTION;

EID: 77949879590     PISSN: 09365214     EISSN: 14372096     Source Type: Journal    
DOI: 10.1055/s-0029-1219396     Document Type: Article

References (24)

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20. 3,4-Bis(trifluoromethylsulfonyloxy)benzophenone (2) To a CH2Cl2 solution (10 mL/mmol) of 1 (1.0 equiv) was added pyridine (4.0 equiv) at 78 C under argon atmosphere. After 10 min, Tf2O (2.4 equiv) was added at 78 C. The mixture was allowed to warm to 0 C during 4 h with stirring. The reaction mixture was filtered, and the filtrate was concentrated in vacuo. The product was isolated by rapid column chromatography (flash silica gel, heptanesEtOAc). Starting with 1 (214 mg, 1.0 mmol), pyridine (0.32 mL, 4.0 mmol), and Tf2O (0.38 mL, 2.4 mmol), 2 was isolated as a highly viscous oil (401 mg, 84%). 1H NMR (300 MHz, CDCl3): d = 7.447.60 (m, 5 H, ArH), 7.687.74 (m, 2 H, ArH), 7.86 (s, 1 H, ArH). 13C NMR (62.89 MHz, CDCl3): d = 115.9 (q, JF,C = 320.0 Hz, CF3), 121.1 (q, JF,C = 321.3 Hz, CF3), 123.6, 125.2, 128.7, 129.9, 130.9, 133.6 (CH), 135.7, 138.7, 140.2, 142.9 (C), 192.6 (C=O). 19F NMR (282 MHz, CDCl3): d = 73.3, 72.0 (2 CF). IR (KBr): n = 3061, (w), 1598, 1589, 1580 (m), 1496, 1431, 1414, 1319, 1291 (m), 1265 (s), 1165, 1077, 1028, 989, 976, 932 (m), 887, 787, 757 (s), 680, 595, 572 (m) cm1. GC-MS (EI, 70 eV): m/z (%) = 478 (74) [M+], 401 (5), 345 (08), 253 (26), 225 (32), 204 (04), 167 (22), 156 (06), 128 (27), 105 (100), 77 (43), 69 (30), 51 (14). HRMS (EI, 70 eV): m/z calcd for C15H8F6O7S2 [M+]: 477.96101; found: 477.960958
21. General Procedure for the Synthesis of 4ai, 5ae, and 6ad The reaction was carried out in a pressure tube. To a dioxane suspension (5 mL) of 2 or 5, Pd(PPh3)4, arylboronic acid, and K3PO4 were added. The mixture was stirred at 110 C under argon atmosphere for the indicated period of time (68 h). The reaction mixture was diluted with H2O and extracted with CH2Cl2 (3 25 mL). The combined organic layers were dried (Na2SO4), filtered, and the filtrate was concentrated in vacuo. The residue was purified by flash chromatography (silica gel, EtOAcheptanes).
22. 3,4-Bis(3,5-dimethylphenyl)benzophenone (4c) Starting with 2 (220 mg, 0.46 mmol), K3PO4 (292 mg, 1.38 mmol), Pd(PPh3)4 (6 mol%), 3,5 dimethylphenylboronicacid (180 mg, 1.2 mmol), and 1,4-dioxane (5 mL per mmol of 2), 4c was isolated as a crystalline solid (134 mg, 75%); mp 140142 C. 1H NMR (250 MHz, CDCl3): d = 2.09 (s, 6 H, 2 CH3), 2.11 (s, 6 H, 2 CH3), 6.676.77 (m, 5 H, ArH), 7.387.48 (m, 5 H, ArH), 7.687.78 (m, 4 H, ArH). 13C NMR (75.46 MHz, CDCl3): d = 21.2 (2 CH3), 21.3 (2 CH3), 125.1, 127.5, 127.7, 128.3, 128.6, 128.8, 130.0, 130.4, 132.1, 132.3 (CH), 136.3, 137.1, 137.2, 137.8, 140.4, 140.5, 140.9, 144.9 (C), 196.4 (C=O). IR (KBr): n = 3289, 3013, 2916, 2857, 2732 (w), 1732, (s), 1574 1505 (m), 1495, 1455, 1436, 1386, 1328, 1296 (m), 1250 (s), 1199, 1118, 1067, 1036, 959, 902 (m), 882, 842, 793, 738 (s), 695, 648, 596, 567 (m) cm1. GC-MS (EI, 70 eV): m/z (%) = 390 (100) [M+], 313 (29), 270 (13), 239 (7), 148 (4), 105 (22), 77 (11). HRMS (EI): m/z calcd for C29H26O [M+]: 390.19782; found: 390.197629.
23. CCDC-759141 contains all crystallographic details of this publication and is available free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html or can be ordered from the following address: Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ, UK; fax: +44 (1223)336033; or deposit@ccdc.cam.ac.uk.
24. 4-(3,4,5-Trimethoxyphenyl)-3-(trifluorosulfonyloxy)- benzophenone (5d) Starting with 2 (220 mg, 0.46 mmol), K3PO4 (146 mg, 0.69 mmol), Pd(PPh3)4 (3 mol%), 3,4,5-trimethoxyphenylboronic acid (125 mg, 0.59 mmol), and 1,4-dioxane (5mL per mmol of triflate), 5d was isolated as a viscous oil (173 mg, 76%); mp 139140 C. 1H NMR (300 MHz, CDCl3): d = 3.82 (s, 6 H, 2 OCH3), 3.83 (s, 3 H, OCH3), 6.62 (s, 2 H, ArH), 7.39 7.47 (m, 3 H, ArH), 7.56 (s, 1 H, ArH), 7.687.78 (m, 3 H, ArH), 7.88 (d, 1 H, J = 6.4 Hz, ArH). 13C NMR (75.47 MHz, CDCl3): d = 56.2 (2 OCH3), 61.0 (OCH3), 106.8 (CH), 120 (q, JF,C = 320 Hz, CF3), 122.0, 128.5, 130.0, 130.4, 133.1, 133.3 (CH), 135.8, 136.7, 137.7, 138.6, 149.0, 153.3 (C), 194.8 (C=O). 19F NMR (282 MHz, CDCl3): d = 73.8 (CF3). IR (KBr): n = 3065, 2999, 2936 (w), 1660, 1609 (s),1584, 1514, 1488 (m), 1463, 1418, 1393, 1317, 1291, 1278 (m), 1241 (s), 1170, 1104, 1063, 1001, 978 (m), 889, 831, 790, 745 (s), 675, 630, 598, 569 (m) cm1. GC-MS (EI, 70 eV): m/z (%) = 496 (92) [M+], 363 (26), 332 (100), 317 (17), 255 (12), 227 (07), 185 (05), 105 (57), 77 (19). HRMS (EI): m/z calcd for C23H19F3O7S [M+]: 496.07981; found: 496.079887.