аЯрЁБс>ўџ 57ўџџџ4џџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџьЅС7 №П!!bjbjUU "27|7|џџџџџџl0000000”8V$z”OЖšš"ММММММЮаааааа$ %2є0МММММє 00ММ    М^0М0МЮ МЮ в ь :F,00ЮМŽ Д0*Р”Š r Ю0O|RW WЮ D.r"0000йANNULATION OF CYCLOHEXANE RING BY TANDEM OF A FREE RADICAL ALKYLATION OF NON-ACTIVATED (-CARBON ATOM AND INTRAMOLECULAR CARBANION CYCLOALKYLATION Goran Petrovic and Zivorad Cekovic* Faculty of Chemistry, University of Belgrade, Studentski trg 16, 11000 Belgrade, Serbia, Yugoslavia Ms. No: o10062401 Supporting Information General experimental procedure for the 4 + 2 cyclohexane ring annulation involving free radical (-alkylation of non-activated carbon atom and subsequent anionic cyclization reaction. Free radical alkylation ov non-activated (-carbon atom A solution of alkyl arenesulfenate ester ( 0.5 mmol), methyl vinyl ketone (0.35 g; 5 mmol; 10 equivalents excess) and tributyltin hydride (0.16 g; 0.55 mmol) in benzene (40 ml) was irradiated at r.t. by visible light (xenon lamp 250 W, ( ( 300 nm or by UV lamp) for 1 h in an argon atmosphere. After reaction was completed benzene was evaporated and residual oil was dissolved in ether (50 ml) and washed with aqueous NaF solution (0.5 g in 10 ml). Ethereal solution was separated and aqueous solution extracted with ether (2 x 20 ml). Ethereal solutions were dried (anh. Na2SO4) and by evaporation of ether an oily alkylation product was obtained, which was dissolved in toluene and purified by dry flash chromatography using petrol ether : acetone 95 : 5 as eluent. Tosylation (or mesylation) of hydroxy ketones To a stirred solution of hydroxy ketones ((-alkylated products) (0.193 mmol), pyridine (0.046 g, 0.58 mmol) in CH2Cl2, p-toluensulfonyl chloride (0.074 g, 0.366 mmol) was added. The reaction was completed after 12 h of stirring at r.t. After standard work up procedure the crude product was purified by dry flash chromatography using petrolether/acetone 95 : 5 to give a pure tosylate. c) Cycloalkylation of keto-sulfonate esters To a solution of tosylate (or mesylate) from the above experiment (0.67 mmol) in DME (0.5 ml) sodium hydride (0.0032 g, 0.134 mmol, as a 80% suspension) was added in an argon atmosphere and the mixture was heated to 80oC during 8 h. After reaction was completed ethanol was added carefully and then water. The mixture was extracted by ether (3 x 25 ml), ethereal solution washed by brine and dried by anh. Na2SO4. Ether was evaporated and oily residue was purified by dry flash chromatography using petrolether/acetone 95 : 5 as eluent to give cyclic ketone as a final product. 3,3-Dimethylcyclohexyl-ethanone [Methyl-(3,3-dimethylcyclohexyl) ketone] (5) 5,5-Dimethyl-8-hydroxyoctan-2-one. This compound was obtained in 41% yield as a colorless oil, according to the described general procedure. IR (film): 3443,1715, 1585, 1472, 1417, 1387, 1366, 1299, 1261, 1223, 1164, 1060,1022, 897, 851, 801, 750, 692 cm –1. 1H-NMR (CDCl3, 200 MHz) (: 0.86 (s, 6H), 1.18-1.27 (m, 2H), 1.44-1.56 (m, 4H), 1.85 (s, broad, 1H), 2.16 (s, 3H), 2.35-2.43 (m, 2H), 3.61 (t, J = 6.4 Hz, 2H). 13C-NMR (CDCl3, 50 MHz) (: 209.83, 63.47, 38.82, 37.44, 35.05, 31.90, 29.84, 27.26, 26.73. 5,5-Dimethyl-8-tosyloxyoctan-2-one. Following the general procedure this compound is prepared as a pale yellow oil (87% yield). IR (film): 1714, 1599, 1495, 1471, 1358, 1292, 1176, 1098, 1020, 968, 913, 816, 733, 665 cm-1. 1H-NMR (CDCl3, 200 MHz) (: 0.81 (s, 6H), 1.12-1.21 (m, 2H), 2.15 (s, 3H), 2.30-2.38 (m, 2H), 2.45 (s, 3H), 4.00 (t, J=6.4 Hz, 2H), 7.57 AA’BB’ system, (A=7.36, (B =7.79, JAB= 8.4 Hz, JAB’ = 1.6 Hz, 4H). 13C-NMR (CDCl3, 50 MHz) (: 209.26, 144.70, 133.04, 129.79, 127.80, 71.25, 38.58, 37.10, 34.79, 31.81, 29.88, 26.48, 23.65, 21.51. 3,3-Dimethylcyclohexyl-ethanone (5). Ketone 5 was obtained as colorless oil according to the described procedure (yield 74%). IR (film): 1748,1462, 1378, 1268, 1164, 779 cm-1. 1H-NMR (CDCl3, 200 MHz) (: 0.92 (s, 3H), 0.94 (s, 3H), 1.02-l.71 (m, 7H), 1.80-1.94 (m, 1H), 2.50 (tt, Jaa = 12.4 Hz, Jae = 3.6 Hz, 1H). 13C-NMR (CDCl3, 50 MHz) (: 212.63 (C), 47.66 (CH), 40.99, 38.51 (CH2), 33.08 (CH3), 30.46 (C), 28.17 (CH2), 27.93, 24.37 (CH3), 21.544 (CH2). MS (CI): 155 (M+1) 100%. 1-(3-Butylcyclohexyl)-ethanon [Methyl-(3-butylcyclohexyl) ketone] (6). 5-(3-Hydroxypropyl)-nonan-2-one. Alkylation of (-carbon atom was carried out following the general procedure and hydroxy ketone was obtained as an oil (35% yield). IR (film): 3418, 1713, 1456, 1413, 1359, 1308, 1266, 1226, 1166, 1059 cm-1. 1H NMR (CDCl3, 200 MHz) (: 0.89 (t, J = 6.8 Hz, 3H), 1.24-1.33 (m, 9H), 1.48-1.64 (m, 4H), 2.15 (s, 3H), 2.38 –2.45 (m, 2H), 3.63 (t, J = 6.6 Hz, 2H). 13C NMR (CDCl3, 50 MHz) (: 209.68 C, (62.87, 40.88) CH2, 36.54 CH3, 32.79 CH2, 29.68 CH, (9.52, 29.13, 28.53, 27.15, 22.84) CH2, 13.89 CH3. 5-(3-Toluensuphonylpropyl)-nonan-2-one. Prepared in 90% yield. IR (film): 1715, 1599, 1456, 1413, 1360, 1307, 1292, 1211, 1189, 1177, 1098, 958, 920, 816, 665 cm-1. 1H NMR (CDCl3, 200 MHz) (: 0.87 (t, J = 6.8 Hz, 3H), 1.18-1.27 (m, 9H), 1.40-l.75 (m, 4H), 2.13 (s, 3H), 2.33-2.41 (m, 2H), 2.45 (s, 3H), 4.01 (t, J = 6.6 Hz, 2H), 7.57 ( AA’BB’ system, (A = 7.35, (B = 7.79, JAB == 8.4 Hz, JAB’ = 0.6 Hz, 4H). 13C NMR (CDCl3, 50 MHz) (: 209.09, 144.65, 133.08, 129.77, 127.78, 70.85, 40.75, 36.24, 32.64, 29.82, 28.89, 28.47, 26.90, 25.87, 22.86, 21.51, 13.94. 1-(3-Butylcyclohexyl)-ethanone. Following the described procedure compound 6 was obtained in 76% yield as a colorless oil. IR (film) : 1712, 1448, 1353, 1259, 1296, 1175, 968 cm-1. 1H NMR (CDCl3, 200 MHz) (: 0.78-1.01 (m, 3H), 1.17-1.39 (m, 10H, 1.68-1.96 (m, 5H), 2.14 (s, 3H), 2.34 (tt, Jaxax =12.0 Hz, Jaxeq = 3.2 Hz, 1H). 13C NMR (CDCl3, 50 MHz) (: 212.45 (C),51.69 (CH), 37.07 (CH3), 37.03, 34.90, 32.55, 28.95, 28.49 (CH2), 27.91, (CH), 25.61, 22.89 (CH2), 14.06 (CH3). 1-Spiro[5.5]undec-2-yl-ethanone (3-Acetyl-spirobicyclohexane)( 8) 4-[1-(3-Hydroxy-propyl)-cyclohexyl]-butan-2-one. Following the general procedure this hydroxy ketone was prepared in 47% as a colorless oil. IR (film) : 3405, 1713, 1596, 1519, 1459, 1416, 1358, 1339, 1164, 1057, 1018, 964, 918, 852, 822 cm-1. 1H-NMR (CDCl3, 200 MHz) (: 0.91 (t, J = 7.2 Hz, 2H), 1.21-1.62 (m, 14H), 1.93 (s, broad, 1H), 2.16 (s, 3H), 2.29-2.38 (M, 2H), 3.61 (t, J = 6.4 Hz, 2H). 13C-NMR (CDCl3, 50 MHz) (: 210.01, 63.52, 37.71, 35.58, 33.92, 32.52, 30.42, 29.88, 27.67, 26.92, 26.27, 26.09, 21.41. 4-[1-(3-p-Toluenesulfonyl-propyl)-cyclohexyl]-butan-2-one. Prepared in 80% yield as a pale yellow oil. IR (film): 2000-1600, 1715, 1599, 1496, 1460, 1359, 1308, 1292, 1211, 1189, 1177. 1120, 1098, 1041, 1020, 990, 945, 922, 817, 793, 736, 665 cm-1. 1H NMR (CDCl3, 200 MHz,) (: 1.16-1.25 (m, 6H), 1.34-1.52 (m, 10H), 2.14 (s, 3H), 2.13-2.32 (m, 2H), 2.45 (s, 3H), 4.01 (t, J = 6.2 Hz, 2H), 7.57 AA’BB’ system, (A = 7.35; (B = 7.79: JAB = 8.4 Hz, JAB’ 0.6 Hz, 4H). 13C NMR (CDCl3, 50 MHz) (: 209.38, 144.71, 133.14, 129.79, 127.83, 71.36, 37.49, 35.36, 33.88, 32.25, 30.09, 29.95, 26.16, 22.59, 21.54, 21.32. 1-Spiro[5.5]undec-2-yl-ethanon (3-Acetyl-spirobicyclohexane) (8 Following the described procedure bicyclic ketone 8 was obtained in 77% yield as a colorless oil. IR (film): 1709, 1451, 1372, 1354, 1270, 1236, 1189, 1164, 964, 903, 843 cm-1. 1H NMR (CDCl3, 200 MHz) (: 0.89-1.90 (m, 18H), 2.13 (s, 3H), 2.50 (tt, Jaxax = 12.2 Hz, Jaxeq= 3.4 Hz, 1H). 13C NMR (CDCl3, 50 MHz) (: 212.84 (C), 46.68 (CH), 41.82, 38.75, 35.83 (CH2), 32.65 (C), 32.14, 28.71 (CH2), 27.93 (CH3), 26.78, 21.47, 20.67 (CH2). MS (CI): 195 (M+1) 100%. PAGE  PAGE 3 WX’“З02JЋЌ,-:;<V)*+,}~€B { Ї Ј ю я ё ђ є і  . 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