3,5-Bis-(trifluoromethyl)phenyl sulfones in the synthesis of 3,5-disubstituted cyclopent-2-enones

Diego A. Alonso; Armin Babrowski; Mónica Fuensanta; Carmen Nájera; Montserrat Varea

doi:10.3998/ark.5550190.0008.519

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3,5-Bis-(trifluoromethyl)phenyl sulfones in the synthesis of 3,5-disubstituted cyclopent-2-enones

Diego A. Alonso; Armin Babrowski; Mónica Fuensanta; Carmen Nájera; Montserrat Varea

Volume 2007, Issue 5, Commemorative Issue in Honor of Prof. Lutz F. Tietze on the occasion of his 65th anniversary, pp. 243-262

DOI: http://dx.doi.org/10.3998/ark.5550190.0008.519

Paper ID: LT-2241HP

Received on 2006-10-31; Accepted on 2007-01-10; Published on 2007-01-26

Permissions: This work is licensed under a Creative Commons Attribution-NonCommercial 3.0 License. Please contact [email protected] to use this work in a way not covered by the license.

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BTFPSO2, 62), 239 (M+-BTFPSO2, 62), 223 (46), 221 (45), 213 (15), 159 (99), 144 (17), 142 (100), 141 (37), 131 (62), 129 (27), 115 (55), 105 (14), 103 (19), 91 (45), 77 (19), 43 (13); HRMS Calcd for C19H15BrF6O3S (M+) 515.9829, found: 515.98.38. (1R*,2R*,4R*)-4-[3,5-Bis-(trifluoromethyl)phenylsulfonyl]-2-bromo-4-(4-nitrophenyl)- cyclopentanol (7bd). White solid; Rf (hexane/EtOAc: 7/3) 0.47; mp 249–250 ºC; IR • 3507, 3081, 2969, 2918, 2842, 1731, 1609, 1513, 1361, 1274, 1142; 1H NMR (CD3COCD3) • 8.41 (s, 1H, ArH), 8.15 (d, J = 8.9, 2H, ArH), 7.76 (s, 2H, ArH), 7.83 (d, J = 8.8, 2H, ArH), 4.91 (d, J = 5.4, 1H, OH) 4.70–4.65 (m, 1H, CHOH), 4.13–4.07 (m, 1H, CHBr), 3.38 (dd, J = 15.1, 8.1, 1H x CH2CHBr), 3.25–3.17 (m, 2H, 1 x CH2CHBr, 1 x CH2CHOH), 2.45 (dd, J = 14.4, 8.4, 1H x CH2CHOH); 13C NMR (100MHz, CD3COCD3) • 148.9, 144.7, 138.1 (ArC), 132.9 (q, JC-F = 35.0, 2 x CCF3), 131.8, 131.2, 129.1, 123.8 (ArCH), 123.4 (q, JC-F = 272.1, 2 x CF3), 79.0 (CHOH), 75.4 (CS), 52.2 (CHBr), 41.1 (CH2CHBr), 40.9 (CH2CHOH); MS m/z 563 (M++2, 0.23), 561 (M+, 0.22), 286 (32), 284 (36), 268 (55), 266 (54), 214 (15), 213 (25), 205 (26), 204 (100), 195 (14), 188 (35), 187 (94), 176 (20), 163 (18), 158 (54), 150 (12), 145 (14), 144 (15), 141 (25), 139 (14), 131 (19), 130 (53), 129 (51), 128 (57), 127 (22), 116 (479, 115 (82), 103 (16), 102 (21), 91 (16), 89 (14), 77 (15), 63 (13), 58 (17), 43 (13); HRMS Calcd for C19H14BrF6NO5S (M+) 560.9680, found: 560.9674. (1R*,3R*,4R*)-Isopropyl 1-[3,5-bis-(trifluoromethyl)phenylsulfonyl]-3-bromo-4-hydroxy- cyclopentanecarboxylate (7cd). Yellow oil; Rf (hexane/EtOAc: 4/1) 0.28; IR • 3478, 3086, 2983, 2921, 1724, 1631, 1358, 1275, 1152; 1H NMR • 8.30 (s, 2H, ArH), 8.18 (s, 1H, ArH), 4.95 (sept., J = 6.2, 1H, OCH), 4.53–4.49 (m, 1H, CHOH), 4.04–3.99 (m, 1H, CHBr), 3.25 (dd, J = 15.1, 7.5, 1H x CH2CHBr), 2.94 (dd, J = 14.3, 6.2, 1H x CH2CHOH), 2.86 (dd, J = 15.0, 7.7, 1H x CH2CHBr), 2.45 (dd, J = 14.4, 5.0, 1H x CH2CHOH), 2.25 (s, 1H, OH), 1.21 (d, J = 6.7, 6H, 2 x CH3); 13C NMR • 166.9 (CO), 139.2 (ArC), 132.8 (q, JC-F = 35.0, 2 x CCF3), 130.4, 127.9 (ArCH), 122.2 (q, JC-F = 273.5, 2 x CF3), 78.9 (CHOH), 76.8 (CS), 71.9 (OCH), 50.5 (CHBr), 38.8 (CH2CHBr), 37.6 (CH2CHOH), 21.2, 21.1 (CH3); MS m/z 467 (M+-OPri, 4.5), 422 (11), 420 (14), 391 (10), 378 (53), 350 (13), 349 (66), 331 (39), 279 (13), 261 (50), 213 (42), 209 (27), 207 (30), 194 (18), 191 (74); 189 (77), 169 (23), 168 (27), 163 (23), 161 (13), 157 (12), 147 (15), 145 (19), 144 (12), 127 (53), 126 (47), 125 (23); 115 (12); 111 (28), 110 (12), 109 (33), 99 (16), 97 (18), 83 (35), 82 (23), 81 (39), 65 (14), 55 (19), 53 (34), 43 (100), 41 (23); HRMS Calcd for C17H17BrF6O5S (M+) 525.9884, (M+-OH) 508.9857 found: 508.9852. (1R*,3R*,4R*)-1-[3,5-Bis-(trifluoromethyl)phenylsulfonyl]-3-bromo-4-hydroxy-1-cyano- cyclopentane (7dd). White solid; Rf (hexane/EtOAc: 2/1) 0.46; mp 120–122 ºC; IR • 3481, 3082, 2934, 2863, 2257, 1623, 1607, 1279, 1148; 1H NMR • 8.48 (s, 2H, ArH), 8.28 (s, 1H, ArH), 4.58– 4.56 (m, 1H, CHOH), 4.22–4.16 (m, 1H, CHBr), 3.10–2.90 (m, 3H, CH2CHBr, 1 x CH2CHOH), 2.60 (s, 1H, OH), 2.29 (dd, J = 14.3, 4.7, 1H, 1 x CH2CHOH); 13C NMR • 137.0 (ArC), 133.7 (q, JC-F = 35.1 2 x CCF3), 130.7, 129.1 (ArCH), 122.0 (q, JC-F = 274.2, 2 x CF3), 117.5 (CN), 78.8 (CS), 64.1 (CHOH), 49.0 (CHBr), 40.6 (CH2CHBr), 39.1 (CH2CHOH); MS m/z 467 (M++2, 1.3), 465 (M+,1.4), 448 (11), 446 (10), 310 (26), 279 (22), 277 (29), 261 (23), 214 (10), 213 (100), 195 (11), 194 (34); 190 (76); 188 (78), 172 (40); 170 (39); 163 (28), 149 (14), 144 (25), 143 (13), 109 (20); 108 (48), 107 (38), 106 (11), 92 (18), 91 (29), 81 (21), 80 (66), 53 (48), 52 (10), 43 (15); HRMS Calcd for C14H10BrNF6O3S (M+) 464.9469, found: 464.9467. (1R*,3R*,4R*)-Diethyl 1-[3,5-bis-(trifluoromethyl)phenylsulfonyl]-3-bromo-4-hydroxy- cyclopentylphosphonate (7ed). Yellow oil; Rf (hexane/EtOAc: 1/1) 0.48; IR • 3396, 3107, 2988, 2937, 1626, 1446, 1358, 1270, 1146, 1028; 1H NMR • 8.44 (s, 2H, ArH), 8.18 (s, 1H, ArH), 4.52–

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