2. General procedure for the addition of Grignard reagents to 1,2-diketones.

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1 S1 Supporting Information for Diradical-Promoted (n+2 1) Ring Expansion: An Efficient Reaction for the Synthesis of Macrocyclic Ketones Georg Rüedi,* Matthias A. berli, Matthias Nagel, and Hans-Jürgen Hansen rganisch-chemisches Institut, University of Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland 1. General Details Flash chromatography: silica gel 60 (Merk), grain size mm. IR Spectra: Perkin-Elmer 1600 Series FT-IR spectrometer. NMR Spectra: Bruker ARX-300 (300/75 MHz) and Avance DRX 600 (600/150 MHz); chemical shifts (d, ppm) relative to CD(H)Cl 3 (7.27/77.00 ppm); for complete assignments of 1 H NMR signals CSY, TCSY, NESY, RESY 2D- or 1D-NMR methods were applied; for complete assignments of 13 C NMR signals HMBC, HSQC, and HSQC-TCSY 2D-NMR methods were employed. GC/MS: Hewlett Packard HP-5971 Series (mass-selective detector; EI, 70 ev). 2. General procedure for the addition of Grignard reagents to 1,2-diketones. To a freshly prepared solution of the corresponding magnesium bromide (90 mmol) in dry THF (180 ml) was added the substrate 1,2-dione (30 mmol) in dry THF (80 ml) at 20 C. After the addition has completed the cooling bath was removed and the resulting cloudy suspension was allowed to warm to C at which the mixture became clear. The resulting solution was then poured into a separatory funnel containing ether (200 ml) and crushed ice. The organic layer was separated, and the aqueous phase extracted with ether (3 150 ml). The combined organic layers were washed with saturated NH 4 Cl and brine, dried over MgS 4, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (1 5% AcEt in hexane). 2-Hydroxy-2-vinylcyclodecanone H The reaction of cyclodecane-1,2-dione (2.19 g, 13.0 mmol) with vinyl magnesium bromide following the general procedure afforded 1.48 g (58%) of the title compound as a colorless oil (GC purity > 98%). IR (film465, 2929, 2873, 1701, 1634, 1473, 1442, 1414, 1398, 1349, 1309, 1272, 1235, 1181, 1155, 1115, 1090, 1047, 1018, 989, 928 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 5.94 (dd, J = 17.0, 10.5, H C(1')), 5.46 (dd, J = 17.0, 1.3, 1 H), 5.16 (dd, J = 10.5, 1.3, 1 H), 4.32 (br. s, 1 H), 3.12 (ddd, J = 17.7, 11.6, 3.7, H a C(10)), (m, 3 H, H a C(9), CH 2 (10),), (m, H a C(3)), (m, 11 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (d, C(1')), (t, C(2')), (s, C(2)), (t), (t), (t), (t), (t), (t), (t), (t). EI-MS: 178 (1, [M H 2 ] + ), 168 (3), 150 (8), 136 (13), 125 (36), 111 (48), 97 (23), 83 (78), 70 (71), 55 (100).

2 S2 2-Hydroxy-2-vinylcycloundecanone H The reaction of cycloundecane-1,2-dione (2.00 g, 11.0 mmol) with vinyl magnesium bromide following the general procedure afforded 1.60 g (69%) of the title compound as a colorless oil (GC purity > 99%). IR (film470, 2928, 2863, 1705, 1636, 1470, 1444, 1402, 1349, 1168, 1145, 1107, 1076, 1016, 994, 929cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 5.98 (dd, J = 17.0, 10.5, H C(1')), 5.47 (dd, J = 17.0, 1.3, 1 H), 5.18 (dd, J = 10.5, 1.3, 1 H), 4.17 (br. s, 1 H), 2.94 (ddd, J = 17.4, 10.4, 2.0, H a C(11)), 2.33 (ddd, J = 17.4, 7.2, 3.1, H b C(11)), (m, 2 H), (m, 1 H), (m, 13 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (d, C(1`)), (t, C(2`)), (s, C(2)), (t), (t), (t, 2 C), (t), (t), (t), (t), (t). EI-MS: 210 (1, M + ), 192 (2), 181 (1), 167 (3), 139 (13), 125 (18), 111 (26), 98 (21), 83 (74), 70 (71), 55 (100). 2-Hydroxy-2-vinylcyclododecanone (6a) H 6a The reaction of cyclododecane-1,2-dione (4.57 g, 23.3 mmol) with vinyl magnesium bromide following the general procedure afforded 4.08 g (78%) of the title compound as colorless crystals. mp C (50:1 hexan/acet). IR (KBr483, 2934, 2868, 2850, 1700, 1471, 1444, 1411, 1344, 1288, 1249, 1175, 1114, 1037, 994, 930cm 1. 1 H NMR (600 MHz, CDCl 3 ) δ 6.01 (dd, J = 17.0, 10.6, H C(1')), 5.49 (dd, J = 17.0, 1.3, 1 H), 5.19 (dd, J = 10.6, 1.3, 1 H), 4.19 (br. s, 1 H), 3.07 (ddd, J = 17.6, 12.0, 3.1, H a C(12)), (m, 2 H, H b C(12), H a C(11)), 2.05 (ddd, J = 14.3, 12.7, 2.1, H a C(3)), 1.70 (ddd, J = 14.3, 12.7, 6.7, H b C(3)), 1.57 (m c, H a C(4)), (m, 13 H), 0.82 (dd, J = 12.7, 1.8, H b C(4)). 13 C NMR (150 MHz, CDCl 3 ) δ (s, C(1)), (d, C(1')), (t, C(2')), (s, C(2)), (t, C(3)), (t, C(12)), (t), (t), (t), (t), (t), (t), (t, C(11)), (t, C(4)). EI-MS: 224 (7, M + ), 181 (9), 167 (7), 153 (8), 139 (9), 125 (14), 111 (27), 97 (32), 83 (95), 70 (56), 55 (100). Anal. calcd for C 14 H 24 2 (224.34): C, 75.00; H, found: C, 74.95; H, Hydroxy-2-vinylcyclopentadecanone H The reaction of cyclopentadecane-1,2-dione (2.38 g, 10.0 mmol) with vinyl magnesium bromide following the general procedure afforded 1.47 g (55%) of the title compound as a colorless oil (GC purity > 99%). IR (film472, 3091, 2932, 2864, 1705, 1636, 1470, 1445, 1403, 1351, 1236, 1162, 1112, 1098, 992, 930, 732 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 5.96 (dd, J = 17.0, 10.5, H C(1')), 5.48 (dd, J = 17.0, 1.3, 1 H), 5.20 (dd, J = 10.5, 1.3, 1 H), 4.12 (br. s, 1 H), 2.72 (ddd, J = 17.4, 7.8, 7.2, H a C(15)), 2.32 (ddd, J = 17.4, 7.9, 6.0, H b C(15)), (m, 1 H), (m, 3 H) (m, 19 H), (m, 1 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (d, C(1')), (t, C(2')), (s, C(2)), (t), (t), (t), (t), (t, 2 C), (t), (t), (t), 26.05

3 S3 (t), (t), (t), (t). EI-MS: 248 (12, [M H 2 ] + ), 207 (19), 191 (7), 135 (14), 121 (15), 109 (37), 95 (53), 83 (58), 70 (49), 55 (100). (E/Z)-2-Hydroxy-2-(prop-1-enyl)cyclododecanone H The reaction of cyclododecane-1,2-dione (2.94 g, 15.0 mmol) with (E/Z)-prop-1-enyl magnesium bromide following the general procedure afforded 3.04 g (85%) of the title compound as a colorless solid (E/Z 1:1). mp C. IR (KBr436, 3021, 2929, 2863, 1718, 1695, 1470, 1444, 1415, 1347, 1287, 1247, 1171, 1142, 1123, 1061, 1034, 974, 900, 739 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 5.89 (dq, J = 15.3, 6.6, H C(2') of (E)-Isomer), (m, 3 H, H 2 C(1'), H C(2') of (Z)-Isomer), 4.18 (br. s, 1 H), 4.16 (br. s, 1 H), (m, 2 H), (m, 1 H), (m, 1 H), 1.71 (dd, J = 6.6, 1.6, CH 3 of (E)-Isomer), 1.62 (dd, J = 6.6, 1.1, CH 3 of (Z)-Isomer), (m, 1 H), (m, 13 H), (m, 1 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1) of (Z)-Isomer), (s, C(1) of (E)- Isomer), (d, C(1') of (E)-Isomer), (d, C(1') of (Z)-Isomer), (d, C(2') of (Z)-Isomer), (d, C(2') of (E)-Isomer), (s, C(2)), (s, C(2)), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t) (t), (t), (q, CH 3 of (E)-Isomer), (q, CH 3 of (Z)-Isomer). EI-MS: 238 (7, M + ), 210 (2), 195 (11), 181 (5), 167 (8), 153 (6), 139 (9), 125 (23), 111 (17), 97 (100), 84 (62), 69 (95), 55(24). Anal. calcd for C 15 H 26 2 (238.37): C, 75.59; H, found: C, 75.69; H, (E/Z)-2-Hydroxy-2-(prop-1-enyl)cyclotetradecanone The reaction of cyclotetradecane-1,2-dione (2.02 g, 9.0 mmol) with (E/Z)-prop-1-enyl H magnesium bromide following the general procedure afforded 1.75 g (73%) of the title compound as a colorless oil (E/Z 1:1) (combined GC purity > 99%). IR (film470, 3019, 2932, 2860, 1705, 1461, 1444, 1053, 1036, 968, 721 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 5.86 (dq, J = 15.3, 6.6, H C(2') of (E)-Isomer), (m, 3 H, CH (1'), 2 H C(2') of (Z)-Isomer), 4.24 (br. s, 1 H), 4.20 (br. s, 1 H), (m, 1 H), (m, 1 H), (m, 3 H), 1.70 (dd, J = 6.6, 1.6, CH 3 of (E)-Isomer), 1.62 (dd, J = 6.8, 1.4, CH 3 of (Z)-Isomer), (m, 1 H), (m, 12 H), (m, 1 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1) of (Z)-Isomer), (s, C(1) of (E)-Isomer), (d, C(1') of (E)-Isomer), (d, C(1') of (Z)-Isomer), (d, C(2') of (Z)-Isomer), (d, C(2') of (E)-Isomer), (s, C(2)), (s, C(2)), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (2 t), (t), (t), (t), (t), (2 t), (t), (t) (t), (t), (q, CH 3 of (E)-Isomer), (q, CH 3 of (Z)-Isomer). EI-MS: 266 (8, M + ), 223 (10), 153 (5), 125 (27), 111 (14), 97 (85), 84 (63), 69 (100), 55 (46).

4 S4 2-Hydroxy-2-isopropenylcyclododecanone H The reaction of cyclododecane-1,2-dione (2.94 g, 15.0 mmol) with isopropenyl magnesium bromide following the general procedure afforded 2.54 g (71%) of the title compound as colorless crystals. mp C (60:1 haxane/acet). IR (KBr451, 3092, 2931, 2866, 1705, 1643, 1471, 1441, 1374, 1345, 1113, 1033, 1010, 898 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 5.24 (s, CH 2 (2')), 5.10 (s, CH 2 (2')), 4.29 (s, 1 H), (m, 1 H), (m, 2 H), (m, 1 H), (m, 1 H), 1.61 (s, CH 3 ), (m, 1 H), (m, 7 H), (m, 1 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (s, C(1')), (t, C(2')), (s, C(2)), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (q, CH 3 ). EI-MS: 238 (16, M + ), 210 (3), 195 (7), 181 (9), 163 (10), 153 (8), 139 (13), 125 (19), 111 (33), 97 (100), 72 (73), 69 (86), 55 (48). Anal. calcd for C 15 H 26 2 (238.37): C, 75.59; H, found: C, 75.42; H, (E)- and (Z)-2-Hydroxy-2-(1-methylprop-1-enyl)cyclododecanone The reaction of cyclododecane-1,2-dione (2.94 g, 15.0 mmol) with (E/Z)-1- H H methylprop-1-enyl magnesium bromide following the general procedure afforded 2.97 g (79%) of the title compound as a colorless oil (E/Z 1:1) (combined GC purity > 98%). An analytical amount of each isomer could be obtained by repeated flash chromatography on silica gel (100 g per g substrate). Data of (E)-isomer: IR (film468, 2931, 1862, 1703, 1469, 1444, 1409, 1350, 1287, 1247, 1164, 1118, 1065, 1016, 984, 839, 819, 718 cm 1. 1 H NMR (600 MHz, CDCl 3 ) δ 5.82 (qd, J = 6.8, 1.3, H C(2')), 4.28 (br. s, 1 H), 3.02 (ddd, J = 18.5, 12.5, 2.7, H a C(12)), (m, 2 H, H a C(3,11)), 1.91 (dt, J = 18.4, 3.6, H b C(12)), 1.81 (td, J = 13.2, 6.5, H b C(3)), 1.68 (dd, J = 6.3, 1.0, CH 3 (3')), (m, H a C(4)), 1.46 (t, J = 1.3, CH 3 (1'')), (m, 14 H), (m, H b C(4)). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (s, C(1')), (d, C(2')), (s, C(2)), (t, C(3)), (t, C(12)), (t), (t), (t), (t), (t), (t), (t, C(11)), (t, C(4)), (q, CH 3 (3')), (q, CH 3 (1'')). EI-MS: 252 (6, M + ), 234 (1), 224 (8), 209 (19), 195 (4), 181 (5), 167 (7), 139 (7), 125 (9), 111 (74), 98 (57), 83 (100), 69 (28), 55 (92). Data of (Z)-isomer: IR (film470, 2930, 1863, 1703, 1469, 1444, 1409, 1349, 1287, 1246, 1163, 1117, 1066, 1024, 994, 917, 871, 836, 817, 717 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 5.53 (qd, J = 7.3, 1.5, H C(2')), 4.22 (br. s, 1 H), (m, H a C(12)), (m, 2 H, H a C(3,11)), (m, 2 H, H b C(3,12)), 1.91 (q, J = 1.5, CH 3 (1'')), (m, H a C(4)), 1.52 (dq, J = 7.3, 1.5, CH 3 (3')), (m, 14 H), (m, H b C(4)). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (s, C(1')), (d, C(2')), (s, C(2)), (t, C(3)), (t, C(12)), (t), (t), (t), (q, CH3), (t), (t), (t), (t), 18.93(t), (q, CH 3 ). EI-MS: 252 (9, M + ), 234 (1), 224 (8), 209 (21), 195 (5), 181 (6), 167 (8), 139 (11), 125 (13), 111 (82), 98 (54), 83 (100), 69 (15), 55 (89).

5 S5 2-Hydroxy-2-(2-methylprop-1-enyl)cyclododecanone The reaction of cyclododecane-1,2-dione (2.94 g, 15.0 mmol) with 2-methylprop-1-enyl H magnesium bromide following the general procedure afforded 3.18 g (84%) of the title compound as colorless crystals. mp C (60:1 hexane/acet). IR (KBr482, 2926, 2853, 1698, 1663, 1467, 1448, 1347, 1110, 1071, 1038, 978, 908, 890, 824, 741 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 5.39 (quint., J = 1.3, H C(1')), 4.13 (br. s, 1 H), (m, 1 H), (m, 2 H), (m, 2 H), 1.72 (d, J = 1.3, CH 3 ), 1.57 (d, J = 1.3, CH 3 ), (m, 14 H), (m, 1 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (s, C(2')), (d, C(1')), (s, C(2)), (t), (t), (q, CH 3 ), (2 t), (t), (t), (t), (t), (t), (t), (q, CH 3 ). EI-MS: 252 (1, M + ), 224 (3), 209 (7), 181 (2), 167 (1), 139 (8), 125 (5), 111 (44), 98 (45), 83 (100), 69 (8), 55 (34). Anal. calcd for C 16 H 28 2 (252.40): C, 76.14; H, found: C, 76.01; H, Ethynyl-2-hydroxycyclododecanone H The reaction of cyclododecane-1,2-dione (2.94 g, 15.0 mmol) with ethynyl magnesium bromide following the general procedure afforded 2.47 g (74%) of the title compound as colorless crystals (GC purity > 99%). mp C (50:1 hexane/acet). IR (KBr492, 3243, 2931, 2863, 1718, 1468, 1449, 1405, 1095, 1071, 1032, 908, 740 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 4.16 (s, 1 H), 3.21 (ddd, J = 18.7, 12.2, 3.6, H a C(12)), 2.58 (ddd, J = 18.7, 5.0, 3.4, H b C(12)), 2.55 (s, H C(2')), (m, 3 H), (m, 14 H), (m, 1 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (s, C(2)), (s, C(1')), (d, C(2')), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t). EI-MS: 222 (1, M + ), 207 (2), 193 (2), 179 (6), 165 (13), 151 (22), 137 (27), 123 (30), 109 (42), 97 (69), 95 (48), 69 (51), 55 (100). 3. General procedure for silylether formation. A solution of the 2-hydroxy ketone (10 mmol), DMAP (0.19 g, 1.5 mmol), and Et 3 N (2.1 ml, 15 mmol) in DMF (40 ml) was cooled to 0 C and TMSCl (1.5 ml, 12 mmol) was added via syringe. The resulting cloudy solution was stirred for 1 h at room temperature and then poured into a separatory funnel containing ether (100 ml) and saturated NH 4 Cl (100 ml). The organic layer was separated, and the aqueous phase extracted with ether (3 100 ml). The combined organic layers were washed with saturated NH 4 Cl and brine, dried over MgS 4, filtered and concentrated under reduced pressure. The residue was filtered through a pad of silica gel. The silyl ethers were immediately subjected to FVP without further purification.

6 S6 2-Trimethylsilyloxy-2-vinylcyclodecanone (10a) TMS 10a The reaction of 2-hydroxy-2-vinylcyclodecanone (0.79 g, 4.03 mmol) following the general procedure afforded 1.07 g (99%) of the title compound as a colorless oil (GC purity > 99%). IR (film) 2929, 2875, 1717, 1474, 1443, 1411, 1249, 1185, 1171, 1131, 1069, 1047, 1020, 987m, 925, 893, 842 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 5.98 (dd, J = 17.2, 10.6, H C(1')), 5.30 (dd, J = 17.2, 1.1, 1 H), 5.15 (dd, J = 10.6, 1.1, 1 H), (m, 2 H), (m, 1 H), (m, 1 H), (m, 2 H), (m, 10 H), 0.17 (s, 9 H, (CH 3 Si). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (d, C(1')), (t, C(2')), (s, C(2)), (t, C(3)), (t, C(10)), (t), (t), (t), (t), (t), (t), 2.65 (q, (CH 3 Si). EI-MS: 253 (9, [M H 2 ] + ), 207 (3), 197 (34), 183 (31), 169 (17), 155 (36), 143 (26), 127 (23), 115 (11), 99 (7), 73 (100), 55 (42). HRMS (EI) calcd for C 15 H 28 2 Si m/z , found m/z Trimethylsilyloxy-2-vinylcycloundecanone (10b) TMS 10b The reaction of 2-hydroxy-2-vinylcycloundecanone (0.84 g, 4.00 mmol) following the general procedure afforded 1.11 g (99%) of the title compound as a colorless oil (GC purity > 98%). IR (film) 2931, 2865, 1720, 1636, 1470, 1444, 1250, 1180, 1147, 1113, 1067, 1051, 989, 966, 924, 881, 841, 755 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 6.04 (dd, J = 17.3, 10.7, H C(1')), 5.30 (dd, J = 17.3, 1.1, 1 H), 5.17 (dd, J = 10.7, 1.1, 1 H), 2.83 (ddd, J = 17.4, 7.8, 3.6, H a C(11)), 2.47 (ddd, J = 17.4, 7.5, 4.8, H b C(11)), 2.06 (dt, J = 14.4, 7.2, H a C(3)), (m, 2 H), (m, 13 H), 0.16 (s, 9 H, (CH 3 Si). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (d, C(1')), (t, C(2')), (s, C(2)), (2 t, C(3,11)), (t), (t), (t), (t), (t), (t), (t), 2.57 (q, (CH 3 Si). EI-MS: 282 (1, M + ), 267 (25), 239 (3), 211 (8), 183 (36), 169 (22), 143 (58), 130 (63), 99 (7), 73 (100), 55 (32). HRMS (EI) calcd for C 16 H 30 2 Si m/z , found m/z Trimethylsilyloxy-2-vinylcyclododecanone (6b) TMS 6b The reaction of 2-hydroxy-2-vinylcyclododecanone (6a) (3.0 g, 13.4 mmol) following the general procedure afforded 3.62 g (99%) of the title compound as a colorless oil. IR (film021, 2934, 2866, 1723, 1686, 1638, 1470, 1444, 1412, 1359, 1249, 1160, 1123, 1047, 991, 912, 925, 841, 753, 683 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 6.24 (dd, J = 17.1, 10.7, H C(1')), 5.45 (dd, J = 17.1, 1.4, 1 H), 5.29 (dd, J = 10.7, 1.4, 1 H), 2.81 (ddd, J = 17.3, 11.9, 3.0, H a C(12)), 2.57 (ddd, J = 14.5, 11.9, 3.3, H b C(12)), (m, 2 H), (m, 2 H), (m, 14 H), 0.25 (s, 9 H, (CH 3 Si). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (d, C(1')), (t, C(2')), (s, C(2)), (t, C(3)), (t, C(12)), (t), (t), (t), (t), (t), (t), (t, C(11)), (t, C(4)), 2.55(q, (CH 3 Si). EI-MS: 296 (11, M + ), 281 (29, [M CH 3 ] + ), 268 (5), 239 (4), 225 (7), 197 (9), 183 (17), 169 (15), 143 (59), 130 (78), 115 (10), 73(100), 55 (28). Anal. calcd for C 17 H 32 2 Si (296.53): C, 68.86; H, found: C, 68.95; H,

7 S7 2-Trimethylsilyloxy-2-vinylcyclopentadecanone (10c) TMS 10c The reaction of 2-hydroxy-2-vinylcyclopentadecanone (0.53 g, 1.99 mmol) following the general procedure afforded 0.66 g (98%) of the title compound as a colorless oil (GC purity > 98%). IR (film) 2930, 2858, 1721, 1460, 1407, 1350, 1250, 1120, 1052, 991, 924, 841, 754, 683 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 5.99 (dd, J = 17.3, 10.7, H C(1')), 5.29 (dd, J = 17.3, 1.1, 1 H), 5.17 (dd, J = 10.7, 1.1, 1 H), (m, 1 H), (m, 1 H), (m, 4 H), (m, 20 H), 0.17 (s, 9 H, (CH 3 Si). 13 C-NMR (75 MHz, CDCl 3 ) δ (s, C1)), (d, C(1')), (t, C(2')), (s, C(2)), (t, C(3)), (t, C(15)), (t), (t), (t), (t), (2 t), (t), (2 t), (t), (t), 2.51 (q, (CH 3 Si). EI-MS: 338 (5, M + ), 323 (13), 267 (4), 253 (2), 207 (8), 183 (7), 155 (24), 143 (84), 130 (90), 95 (12), 73 (100), 55 (38). HRMS (EI) calcd for C 20 H 38 2 Si m/z , found m/z (E/Z)-2-(Prop-1-enyl)-2-trimethylsilyloxycyclododecanone (10d) The reaction of (E/Z)-2-hydroxy-2-(prop-1-enyl)cyclododecanone (1.50 g, 6.29 mmol) TMS 10d following the general procedure afforded 1.93 g (99%) of the title compound as a colorless oil (E/Z 1:1). IR (film474, 3021, 2932, 2864, 1720, 1469, 1444, 1409, 1356, 1285, 1247, 1169, 1123, 1071, 1036, 1004, 996, 914, 840, 752 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ (m, 2 H), (m, 2 H), (m, 2 H), (m, 2 H), 1.71 (d, CH 3 ), 1.63 (d, CH 3 ), (m, 14 H), 0.13 (s, 9 H, (CH 3 Si). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (s, C(1)), (d), (d), (d), (d), (s, C(2)), (s, C(2)), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (q, CH 3 ), (q, CH 3 ), 0.47 (q, (CH 3 Si), 0.35 (q, (CH 3 Si). EI-MS: 310 (2, M + ), 282 (11), 267 (9), 253 (3), 239 (6), 211 (5), 197 (17), 169 (78), 157 (15), 130 (33), 115 (3), 73 (100), 55 (28). Anal. calcd for C 18 H 34 2 Si (310.55): C, 69.62; H, found: C, 69.49; H, (E/Z)-2-(Prop-1-enyl)-2-trimethylsilyloxycyclotetradecanone (10e) The reaction of (E/Z)-2-hydroxy-2-(prop-1-enyl)cyclotetradecanone (1.07 g, 4.02 mmol) TMS 10e following the general procedure afforded 1.34 g (99%) of the title compound as a colorless oil (E/Z 1:1) (combined GC purity > 99%). IR (film) 2931, 2859, 1721, 1461, 1444, 1406, 1367, 1350, 1249, 1118, 1076, 968, 891, 841, 754, 717, 702, 682 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ (m, 2 H, H C(1',2')), (m, 1 H), (m, 10 H), (m, 16 H), 0.14 (s, 9 H, (CH 3 Si). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1) of (Z)-Isomer), (s, C(1) of (E)-Isomer), (d, C(1') of (E)-Isomer), (d, C(1') of (Z)-Isomer), (d, C(2') of (Z)-Isomer), (d, C(2') of (E)-

8 S8 Isomer), (s, C(2)), (s, C(2)), (t), (t), (t), (t), (2 t), (2 t), (2 t), (t), (t), (t), (t), (2 t), (2 t), (2 t), (t), (t), (t), 20.92(t), (q, CH 3 of (E)-Isomer), (q, CH 3 of (Z)-Isomer), 2.64 (q, (CH 3 Si), 2.31 (q, (CH 3 Si). EI-MS: 323 (8, [M CH 3 ] + ), 310 (11), 267 (5), 211 (6), 197 (17), 169 (46), 157 (16), 130 (23), 95 (6), 73 (100), 55 (27). HRMS (EI) calcd for C 20 H 38 2 Si m/z , found m/z Isopropenyl-2-trimethylsilylcyclododecanone (10f) TMS 10f The reaction of (E/Z)-2-hydroxy-2-isopropenylcyclododecanone (1.50 g, 6.29 mmol) following the general procedure afforded 1.94 g (99%) of the title compound as a colorless oil. IR (film) 2934, 2865, 1718, 1643, 1469, 1444, 1409, 1247, 1170, 1155, 1029, 904, 840, 753, 680 cm 1. 1 H-NMR (300 MHz, CDCl 3 ) δ 5.28 (s, CH 2 (2')), 5.16 (s, CH 2 (2')), (m, 1 H), (m, 2 H), (m, 1 H), (m, 1 H), 1.65 (s, CH 3 ), (m, 14 H), (m, 1 H), 0.13 (s, 9 H, (CH 3 Si). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (s, C(1')), (t, C(2')), (s, C(2)), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (q, CH 3 ), 2.79 (q, (CH 3 Si). EI-MS: 310 (3, M + ), 295 (11), 282 (7), 253 (4), 239 (5), 211 (3), 183 (9), 169 (38), 144 (71), 95 (7), 73 (100), 55 (28). Anal. calcd for C 18 H 34 2 Si (310.55): C, 69.62; H, found: C, 69.60; H, (E/Z)-2-(1-Methylprop-1-enyl)-2-trimethylsilyloxycyclododecanone (10g) The reaction of 2-hydroxy-2-(1-methylprop-1-enyl)cyclododecanone (2.52 g, 9.98 mmol) TMS 10g following the general procedure afforded 3.22 g (99%) of the title compound as a colorless oil (E/Z 1:1) (combined GC purity > 97%). IR (film) 2932, 2864, 1718, 1673, 1469, 1444, 1409, 1248, 1167, 1077, 1040, 839, 753 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 5.59 (qd, J = 7.7, 1.3, H C(2') of (E)-Isomer), 5.33 (qd, J = 7.3, 1.4, H C(2') of (Z)-Isomer), (m, 1 H), (m, 1 H), (m, 2 H), 1.78 (m c, CH 3 (1'') of (Z)-Isomer), (m, 2 H), 1.52 (d, J = 7.7, CH 3 (3') of (E)-Isomer), 1.41 (d, J = 7.3, CH 3 (3') of (Z)-Isomer), 1.36 (m c, CH 3 (1'') of (E)-Isomer), (m, 13 H), (m, 1 H) (s, 9 H, (CH 3 Si). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1) of (E)-Isomer), (s, C(1) of (E)-Isomer), (s, C(1') of (E)-Isomer), (d, C(2') of (Z)-Isomer), (s, C(1') of (Z)-Isomer), (d, C(2') of (E)-Isomer), (s, C(2) of (E)-Isomer), (s, C(2) of (Z)-Isomer), (t), (t), (t), (t), (t), (t), (t), (t), (2 t), (q, CH 3 of (Z)-Isomer), (t), (2 t), (t), (t), (2 t), (t), (t), (t), (t), (q, CH 3 of (Z)-Isomer), (q, CH 3 of (E)-Isomer), (q, CH 3 of (E)-Isomer), 2.62 (q, (CH 3 Si). EI-MS: 324 (2, M + ), 309 (12), 296 (25), 281 (38), 253 (5), 239 (3), 225 (1), 197 (4), 183 (49), 155 (36), 144 (43), 109 (4), 83 (15), 73 (100), 55 (39). HRMS (EI) calcd for C 19 H 36 2 Si m/z , found m/z

9 S9 2-(2-Methylprop-1-enyl)-2-trimethylsilyloxycyclododecanone (10h) The reaction of 2-hydroxy-2-(2-methylprop-1-enyl)cyclododecanone (1.77 g, 7.01 mmol) TMS 10h following the general procedure afforded 2.27 g (100%) of the title compound as a colorless oil (GC purity > 98%). IR (film) 2931, 2865, 1720, 1469, 1445, 1409, 1376, 1356, 1285, 1166, 1123, 1076, 1037, 1015, 865, 839, 753 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 5.35 (t, J = 1.3, H C(1')), (m, 2 H), (m, 2 H), 1.63 (d, J = 1.3, CH 3 ), 1.47 (d, J = 1.3, CH 3 ), (m, 16 H), 0.10 (s, 9 H, (CH 3 Si). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (s, C(2')), (d, C(1')), (s, C(2)), (t), (t), (t), (t), (q, CH 3 ), (t), (t), (2 t), (t), (q, CH 3 ), (t), 2.24 (q, (CH 3 Si). EI-MS: 309 (8, [M CH 3 ] + ), 281 (31), 253 (5), 225 (3), 211 (18), 183 (79), 170 (24), 155 (37), 130 (3), 83 (16), 73 (100), 55 (29). HRMS (EI) calcd for C 19 H 36 2 Si m/z , found m/z Ethynyl-2-trimethylsilyloxycyclododecanone (13) TMS 13 The reaction of 2-ethynyl-2-hydroxycyclododecanone (1.78 g, 8.01 mmol) following the general procedure afforded 2.35 g (100%) of the title compound as a colorless oil. IR (film309, 2934, 2866, 2111, 1732, 1683, 1469, 1444, 1249, 1168, 1141, 1119, 1087, 1034, 998, 910, 844, 755 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ (m, H a C(12)), (m, H b C(12)), 2.64 (s, H C(2')), (m, 2 H), (m, 2 H), (m, 14 H), 0.19 (s, 9 H, (CH 3 Si). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (s, C(2)), (s, C(1')), (s, C(2')), (t), (t), (t), (t), (t), (t), (2 t), (t), (t), 1.57 (q, (CH 3 Si). EI-MS: 294 (23, M + ), 266 (1), 251 (5), 237 (6), 209 (4), 195 (12), 169 (48), 153 (22), 141 (18), 125 (15), 111 (13), 83 (29), 73 (100), 55 (34). Anal. calcd for C 17 H 30 2 Si (294.51): C, 69.33; H, found: C, 69.45; H, General procedure for thermal rearrangements by FVP. 1,2 The FVP-device consists of an electrically heatable tube furnace (one meter-long), a condenser unit with a cooling trap at the outlet side and a kugelrohr oven as the evaporation unit at the inlet side. A quartz tube (110 cm long, 2.5 cm i. d., no fillings were used), which fitted into the furnace, was connected to a trap (cooled with liquid N 2 ) on one side and to a bulb placed in the kugelrohr oven on the other. The starting material was placed in the bulb equipped with a capillary inlet device for the inert flow gas (a flow of N 2 was adjusted from L/h) and a magnetic stirrer. After evacuation of the apparatus with a highvacuum oil pump ( mbar) the starting material was distilled directly through the preheated reactor tube (1 3 g/h). After all of the starting material had been distilled, the apparatus was vented and the frozen products were transferred to a bulb using Et 2 as solvent. The resulting solution was dried over anhydrous

10 S10 MgS 4 and evaporated under reduced pressure. The residue was dissolved in EtH and treated with 1% HCl to cleave the TMS-group. Workup in the usual manner followed by flash chromatography on silica gel (1 5% AcEt in hexane) provided analytically pure compounds. Cyclotridecanone (7), Cyclotetradecane-1,4-dione (8), 3,4 Cyclotetradecane-1,2-dione (9) FVP of 2-hydroxy-2-vinylcyclododecanone (6a) (3.60 g, 16.2 mmol) at 600 C following the general procedure, but without treatment of the crude product with 1% HCl in EtH afforded 7 (1.46 g, 46%), 8 (0.79 g, 22%), and 9 (0.18 g, 5%). Alternatively, compounds 7 and 8 were prepared in 75 and 14% yield, respectively, upon FVP of 2- trimethylsilyloxy-2-vinylcyclododecanone (6b) at 580 C according to the general procedure (including subsequent treatment with 1% HCl in EtH). Physical and spectral data of 7 are identical in all respects with an authentic sample that is commercially available. Data of 8: mp C (40:1 hexane/acet). IR (KBr) 2930, 2863, 1703, 1466, 1443, 1410, 1375, 1284, 1220, 1205, 1115, 1099, 1006, 974, 899, 765, 716 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 2.71 (s, 4 H, CH 2 (2,3)), 2.48 (t, J = 6.3, 4 H, CH 2 (5,14)), 1.66 (quint., J = 6.3, 4 H, CH 2 (6,13)), (m, 8 H), (m, 4 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1,4)), (t, C(2,3)), (t, C(5,14)), (2 t), (2 t), (2 t), (t, C(6,13)). EI-MS: 224 (11, M + ), 206 (3), 181 (13), 169 (7), 153 (10), 139 (13), 127 (25), 111 (68), 98 (33), 83 (35), 71 (73), 5(100). Anal. calcd for C 14 H 24 2 (224.34): C, 75.00; H, found: C, 74.92; H, Data of 9: IR (KBr397, 2928, 2860, 1707, 1462, 1442, 1413, 1379, 1281, 1260, 1180, 1150, 1092, 1013, 899, 796, 705 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 2.76 (t, J = 6.3, 4 H, CH 2 (3,14)), (m, 4 H, CH 2 (4,13)), (m, 16 H). 13 C-NMR (75 MHz, CDCl 3 ) δ (s, C(1,2)), (t, C(3,14)), (t, 2 C), (t, 2 C), (t, 2 C), (t, 2 C), (2 t). EI-MS: 224 (15, M + ), 139 (13), 125 (21), 112 (28), 98 (63), 71 (59), 58 (74), 55 (100). Cycloundecanone (11a) and Cyclododecane-1,4-dione (12a) 4,6 11a 12a FVP of 2-trimethylsilyloxy-2-vinylcyclodecanone (10a) (1.90 g, 7.08 mmol) at 590 C following the general procedure afforded 11a (0.75 g, 63%) and 12a (0.16 g, 12%). Physical and spectral data of 11a are identical in all respects with an authentic sample that is commercially available. Data of 12a: IR (KBr) 2931, 2865, 1708, 1472, 1442, 1420, 1366, 1316, 1264, 1237, 1226, 1200, 1185, 1152, 1127, 1112, 1069, 1055, 910 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 2.76 (s, 4 H, CH 2 (2,3)), 2.44 (t, J = 6.3, 4 H, CH 2 (5,12)), (quint., J = 6.3, 4 H, CH 2 (6,11)), (m, 4 H), (m, 4 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1,4)), (t, C(2,3)), (t, C(5,12)), (2 t), (2 t), (t, C(6,11)). EI-MS: 196 (2, M + ), 168 (37), 153 (13), 136 (18), 122 (21), 111 (100), 98 (52), 83 (39), 71 (44), 55 (92).

11 S11 Cyclododecanone (11b) and Cyclotridecane-1,4-dione (12b) 4 11b 12b FVP of 2-trimethylsilyloxy-2-vinylcycloundecanone (10b) (0.57 g, 2.02 mmol) at 580 C following the general procedure afforded 11b (0.26 g, 71%) and 12b (71 mg, 17%). Physical and spectral data of 11b are identical in all respects with an authentic sample that is commercially available. Data of 12b: IR (film) 2931, 2862, 1708, 1464, 1441, 1408, 1364, 1319, 1252, 1206, 1108, 1065 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 2.71 (s, 4 H, CH 2 (2,3)), 2.45 (t, J = 6.3, 4 H, CH 2 (5,13)), 1.61 (quint., J = 6.3, 4 H, CH 2 (6,12)), (m, 10 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1,4)), (t, C(2,3)), (t, C(5,13)), (2 t), (2 t), (t, C(9)), (t, C(6,12)). EI-MS: 210 (13, M + ), 192 (5), 182 (10), 167 (18), 150 (21), 139 (27), 127 (32), 111 (87), 98 (49), 83 (37), 71 (64), 55 (100). Cyclohexadecanone (11c) and Cycloheptadecane-1,4-dione (12c) 11c 12c FVP of 2-trimethylsilyloxy-2-vinylcyclopentadecanone (10c) (0.51 g, 1.51 mmol) at 560 C following the general procedure afforded 11c (0.25 g, 70%) and 12c (72 mg, 18%). Data of 11c: IR (film) 2928, 2856, 1712, 1460, 1409, 1365, 1265, 1088 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 2.41 (t, J = 6.8, 4 H, CH 2 (2,16)), 1.64 (m c, 4 H, CH 2 (3,15)), 1.30 (m c, 22 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (t, C(2,16)), (2 t), (2 t), (2 t), (t, C(9)), (4 t), (t, C(3,15)). EI-MS: 238 (25, M + ), 207 (29), 149 (18), 138 (15), 125 (34), 111 (37), 95 (49), 83 (41), 71 (96), 55 (100). Data of 12c: IR (film) 2928, 2856, 1712, 1459, 1406, 1367, 1260, 1069, 732 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 2.66 (s, 4 H, CH 2 (2,3)), 2.47 (t, J = 6.3, 4 H, CH 2 (5,17)), (m, 4 H, CH 2 (6,16)), (m, 18 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1,4)), (t, C(2,3)), (t, C(5,17)), (2 t), (6 t), (t, C(11)), (t, C(6,16)). EI-MS: 266 (24, M + ), 248 (2), 223 (7), 207 (22), 181 (9), 167 (5), 153 (8), 127 (42), 114 (59), 95 (37), 83 (40), 71 (56), 55 (100). Anal. calcd for C 17 H 30 2 (266.42): C, 76.64; H, found: C, 76.80; H, Methylcyclotridecanone (11d) 7 and 2-Methylcyclotetradecane-1,4-dione (12d) 11d 12d FVP of (E/Z)-2-(prop-1-enyl)-2-trimethylsilyloxyclododecanone (10d) (0.47 g, 1.51 mmol) at 560 C following the general procedure afforded 11d (0.23 g, 71%) and 12d (54 mg, 15%). Data of 11d: IR (film) 2929, 2860, 1709, 1461, 1407, 1363, 1282, 1171, 1156, 1123 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ (m, CH 2 (13)), 2.39 (dd, J = 14.1, 4.2, H a C(2)), 2.21 (dd, J = 14.1, 3.7, H b C(2)), (m, H C(3)), (m, CH 2 (12)), (m, 16 H), 2.88 (d, J = 6.8, CH 3 ). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (t, C(2)), (t, C(13)), (t), (d, C(3)), (t), (t), (t), (t), (t), 24.23

12 S12 (t), (t), (t), (q, CH 3 ). EI-MS: 210 (17, M + ), 195 (4), 163 (5), 152 (9), 135 (7), 125 (22), 111 (16), 97 (36), 85 (68), 69 (61), 55 (100). Data of 12d: mp C (40:1 hexane/acet). IR (KBr) 2931, 2899, 2868, 1699, 1468, 1455, 1438, 1417, 1375, 1284, 1255, 1152, 1085, 1027, 729 cm 1. 1 H NMR (600 MHz, CDCl 3 ) δ 3.22 (ddq, J = 10.0, 7.2, 3.5, H C(2)), 3.04 (dd, J = 16.8, 10.0, H a C(3)), 2.58 (ddd, J = 17.6, 9.3, 4.1, H a C(5)), 2.53 (ddd, J = 17.0, 9.4, 3.6, H a C(14)), 2.45 (ddd, J = 17.6, 7.0, 4.2, H b C(5)), 2.37(ddd, J = 17.0, 7.6, 3.7, H b C(14)), 2.20 (dd, J = 16.8, 3.5, H b C(3)), (m, 2 H, H a C(6), H a C(13)), (m, 2 H, H b C(6), H b C(13)), (m, 2 H, H a C(7), H a C(12)), (m, 4 H, CH 2 (9,10)), (m, 6 H, H b C(7), H b C(12), CH 2 (8,11)), 1.08 (d, J = 7.2, CH 3 ). 13 C NMR (150 MHz, CDCl 3 ) δ (s, C(1)), (s, C(4)), (t, C(3)), (t, C(14)), (d, C(2)), (t, C(5)), (t, C(12)), (t, C(7)), (t), (t), (t, C(8,11)), (t, C(13)), (t, C(6)), (q, CH 3 ). EI-MS: 238 (26, M + ), 210 (2), 195 (12), 181 (4), 169 (7), 153 (5), 141 (10), 125 (47), 112 (21), 97 (32), 85 (48), 69 (43), 55 (100). Anal. calcd for C 15 H 26 2 (238.37): C, 75.59; H, found: C, 75.25; H, Methylcyclopentadecanone (11e) 8 and 2-Methylcyclohexadecane-1,4-dione (12e) 11e 12e FVP of (E/Z)-2-(prop-1-enyl)-2-trimethylsilyloxyclotetradecanone (10e) (0.68 g, 2.01 mmol) at 570 C following the general procedure afforded 11e (0.35 g, 73%) and 12e (0.10 g, 19%). Data of 11e: IR (film) 2927, 2856, 1711, 1459, 1408, 1367, 1276, 1128, 1056 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ (m, 3 H, H a C(2), CH 2 (15)), 2.28 (dd, J = 15.0, 5.2, H b C(2)), 2.06 (m c, H C(3)), (m, CH 2 (14)), (m, 20 H), 0.94 (d, J = 6.7, H 3 C). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (t, C(2)), (t), (t), (d, C(3)), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (q, CH 3 ). EI-MS: 232 (20, M + ), 223 (8), 209 (15), 195 (4), 180 (7), 163 (5), 149 (7), 135 (13), 125 (29), 111 (22), 97 (41), 85 (73), 69 (54), 55 (100). Data of 12e: IR (film) 2929, 2856, 1709, 1458, 1407, 1360, 1265, 1172, 1152, 1086, 1033, 916, 733 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 3.15 (ddq, J = 10.4, 7.2, 3.3, H C(2)), 3.04 (dd, J = 17.1, 10.4, H a C(3)), 2.65 (ddd, J = 17.1, 10.0, 3.1, H a C(5)), 2.57 (ddd, J = 16.6, 6.7, 3.6, H a C(16)), 2.46 (ddd, J = 17.1, 7.0, 3.4, H b C(5)), 2.31(ddd, J = 16.6, 7.5, 3.3, H b C(16)), 2.24 (dd, J = 17.1, 3.1, H b C(3)), (m, 2 H), (m, 2 H), (m, 16 H), 1.07 (d, J = 7.1, CH 3 ). 13 C NMR (150 MHz, CDCl 3 ) δ (s, C(1)), (s, C(4)), (t, C(3)), (t, C(16)), (d, C(2)), (t, C(5)), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t), (q, CH 3 ). EI-MS: 266 (35, M + ), 248 (2), 238 (1), 223 (18), 195 (8), 181 (5), 167 (4), 153 (7), 125 (40), 97 (38), 85 (63), 69 (54), 55 (100). Anal. calcd for C 17 H 30 2 (266.42): C, 76.64; H, found: C, 76.52; H,

13 S13 2-Methylcyclotridecanone (11f) 7 and 2-Methylcyclotetradecane-1,4-dione (12f = 12d) 11f 12f FVP of 2-isopropenyl-2-trimethylsilyloxyclododecanone (10f) (0.90 g, 2.90 mmol) at 580 C following the general procedure afforded 11f (0.37 g, 60%) and 12f (83 mg, 12%). Data of 11f: mp C (40:1 hexane/acet). IR (film): 2939, 2861, 1709, 1460, 1407, 1374, 1111, 1086, 1076, 1039, 1025, 1009, 967, 729 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ (m, 2 H, H C(2), H a C(13)), 2.34 (ddd, J = 16.4, 7.5, 3.9, H b C(13)), (m, H a C(12)), (m, H a C(3)), (m, H b C(12)), (m, H b C(3)), (m, 16 H), 1.05 (d, J = 16.9, H 3 C). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (d, C(2)), (t, C(13)), (t, C(3)), (t), (t), (t), (t), (t), (t), (t), (t), (t, C(12)), (q, CH 3 ). EI-MS: 210 (21, M + ), 196 (1), 181 (13), 163 (8), 153 (6), 139 (16), 125 (11), 111 (19), 98 (29), 85 (34), 72 (62), 55 (100). Anal. calcd for C 14 H 26 (210.36): C, 79.94; H, found: C, 79.79; H, ,3-Dimethylcyclotridecanone (11g) and 2,3-Dimethylcyclotetradecane-1,4-dione (12g) 11g 12g FVP of (E/Z)-2-(1-methylprop-1-enyl)-2-trimethylsilyloxyclododecanone (10g) (2.00 g, 6.16 mmol) at 580 C following the general procedure afforded 11g (1.12 g, 81%) and 12g (0.17 g, 11%). Both compounds were obtained as a 1:1 mixture of diastereoisomers. Crystallization afforded in the case of 11g a pure sample of one isomer. In the case of 12g, both isomers could be separated by crystallization. Data of 11g (isomer 1): mp C (50:1 hexane/acet). IR (KBr): 2927, 2861, 2673, 1709, 1691, 1462, 1447, 1406, 1252, 1200, 1166, 1003 cm 1. 1 H NMR (600 MHz, CDCl 3 ) δ 2.69 (ddd, J = 18.2, 9.9, 2.9, H a C(13)), 2.52 (qd, J = 6.9, 2.7, H C(2)), 2.34 (ddd, J = 18.2, 7.5, 3.0, H b C(13)), (m, H C(3)), (m, H a C(12)), (m, H b C(12)), (m, 2 H), (m, 14 H), 1.01 (d, J = 6.9, CH 3 C(2)), 0.96 (d, J = 6.9, CH 3 C(3)). 13 C NMR (150 MHz, CDCl 3 ) δ (s, C(1)), (d, C(2)), (t, C(13)), (d, C((3)), (t), (t), (t), (t), (t), (t), (t), (t), (t, C(12)), (q, CH 3 C(3)), 8.90 (q, CH 3 C(2)). EI-MS: 224 (11, M + ), 209 (8), 195 (23), 181 (1), 167 (13), 152 (7), 139 (28), 125 (19), 111 (30), 97 (33), 83 (46), 70 (57), 55 (100). Anal. calcd for C 15 H 28 (224.39): C, 80.29; H, found: C, 80.33; H, Data of 12g (isomer 1): mp C (50:1 hexane/acet). IR (KBr) 2942, 2860, 1702, 1466, 1455, 1445, 1414, 1404, 1375, 1007 cm 1. 1 H NMR (600 MHz, CDCl 3 ) δ (m, 2 H, H C(2,3)), (m, 4 H, CH 2 (5,14)), (m, 2 H, H a C(6,13)), (m, 14 H), 1.04 (d, J = 6.8, 6 H, CH 3 ). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1,4)), (d, C(2,3)), (t, C(5,14)), (2 t), (2 t), (2 t), (t, C(6,13)), (q, 2 H 3 C). EI-MS: 252 (22, M + ), 224 (13), 209 (26), 139 (38), 125 (22), 111 (41), 99 (48), 83 (59), 69 (50), 55 (100). Anal. calcd for C 16 H 28 2 (224.39): C, 76.14; H, found: C, 76.21; H, Data of 12g (isomer 2): mp C (50:1 hexane/acet). IR (KBr) 2928, 2858, 1703, 1463, 1404, 1372, 1281, 1259, 1149, 1118, 1080, 1035, 1010 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ (m, 2 H,

14 S14 H C(2,3)), (m, 4 H, CH 2 (5,14)), (m, 2 H, H a C(6,13)), (m, 14 H), 1.09 (d, J = 7.1, 6 H, CH 3 ). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1,4)), (d, C(2,3)), (t, C(5,14)), (2 t), (2 t), (2 t), (t, C(6,13)), (q, H 3 C). EI-MS: 252 (16, M + ), 209 (11), 207 (19), 139 (36), 126 (19), 98 (42), 83 (73), 69 (43), 55 (100). 3,3-Dimethylcyclotridecanone (11h) 7 and 2,2-Dimethylcyclotetradecane-1,4-dione (12h) 11h 12h FVP of 2-(2-methylprop-1-enyl)-2-trimethylsilyloxyclododecanone (10h) (1.77 g, 7.01 mmol) at 580 C following the general procedure afforded 11h (1.10 g, 70%) and 12h (0.25 g, 14%). Data of 11h: IR (film) 2930, 2861, 1711, 1622, 1463, 1404, 1363, 1067 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ (m, CH 2 (13)), 2.34 (s, CH 2 (2)), (m, CH 2 (12)), (m, 18 H), 0.99 (s, 6 H, CH 3 ). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (t, C(2)), (t), (t), (s, C(3)), (2 q, CH 3 ), (t), (t), (t), (t), (t), (t), (t), (t). EI-MS: 224 (8, M + ), 209 (5), 181 (2), 166 (6), 142 (7), 125 (30), 111 (35), 98 (38), 83 (57), 69 (69), 55 (100). Data of 12h: mp C (40:1 hexane/acet). IR (KBr): 2991, 2970, 2929, 2864, 1708, 1697, 1620, 1471, 1459, 1448, 1434, 1417, 1376, 1367, 1343, 1115 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 2.81 (s, CH 2 (3)), (m, 4 H, CH 2 (5,14)), (m, 4 H, CH 2 (6,13)), (m, 12 H), 1.17 (s, 6 H, CH 3 ). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (s, C(4)), (t, C(3)), (s, C(2)), (t, C(14)), (t, C(5)), (t), (t), (t), (2 q, CH 3 ), (t), (t), (t), (t), (t). EI-MS: 252 (18, M + ), 224 (9), 209 (14), 196 (3), 169 (7), 153 (8), 139 (12), 125 (36), 111 (45), 98 (93), 83 (41), 69 (37), 55 (100). Anal. calcd for C 16 H 28 2 (252.40): C, 76.14; H, found: C, 76.05; H, (E)- and (Z)-Cyclotridec-2-enone (14) 9 (E)-14 (Z)-14 FVP of 2-ethynyl-2-trimethylsilyloxycyclododecanone (13) (0.59 g, 2.00 mmol) at 540 C following the general procedure afforded recovered 2-ethynyl-2- hydroxycyclododecanone (86 mg, 22%) and (E/Z)-14 (0.13 g, 33%). An analytical amount of each isomer could be obtained by repeated flash chromatography on silica gel (100 g per g substrate). Data of (E)-14: IR (film) 2931, 2859, 1691, 1664, 1625, 1461, 1446, 1348, 1285, 1236, 1214, 739 cm 1. 1 H NMR (300 MHz, CDCl 3 ) δ 6.84 (dt, J = 15.7, 7.6, H C(3)), 6.22 (dt, J = 15.7, 1.2, H C(2)), 2.50 (t, J = 6.5, CH 2 (13)), (m, CH 2 (4)), (m, CH 2 (12)), (m, CH 2 (5)), (m, 12 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (d, C(3)), (d, C(2)), (t), (t), (t), (t), (t), (t), (t), (t), (t), (t). EI-MS: 194 (37, M + ), 136 (9), 111 (19), 109 (42), 95 (63), 81 (98), 67 (100), 55 (60).

15 S15 Data of (Z)-14: 1 H NMR (300 MHz, CDCl 3 ) δ (m, H C(3)), 6.07 (dt, J = 15.9, 1.5, H C(2)), 2.51 (t, J = 6.5, CH 2 (13)), (m, CH 2 (4)), (m, CH 2 (12)), (m, CH 2 (5)), (m, 12 H). 13 C NMR (75 MHz, CDCl 3 ) δ (s, C(1)), (d, C(3)), (d, C(2)), (t), (t), (t), (t), (t), (t), (t), 25.38(t), (t), (t). EI-MS: 194 (21, M + ), 136 (12), 111 (26), 109 (61), 95 (74), 81 (100), 67 (87), 55 (73). 5. References (1) Rüedi, G.; Nagel, M.; Hansen, H.-J., rg. Lett. 2003, 5, (2) McNab, H., Contemp. rg. Synth. 1996, 3, 373. (3) Hadj-Abo, F.; Bienz, S.; Hesse, M., Tetrahedron 1994, 50, (4) Kulkowit, S.; McKervey, M. A., J. Chem. Soc., Chem. Commun. 1978, (5) Prelog, V.; Polyak, P., Helv. Chim. Acta 1957, 40, 816. (6) Barton, D. H. R.; Csuhai, E.; zbalik, N., Tetrahedron 1990, 46, (7) Nagel, M.; Fráter, G.; Hansen, H.-J., Synlett 2002, 280. (8) Yamamoto, T.; gura, M.; Kanisawa, T., Tetrahedron 2002, 58, (9) Satoh, T.; Hayashi, Y.; Mizu, Y.; Yamakawa, K., Tetrahedron Lett. 1992, 33, 7181.