F. Lacombe et al. / Tetrahedron 60 (2004) 7315–7324
7321
53.4, 53.1, 51.2, 51.2, 47.4, 47.3, 38.0, 37.6, 37.3, 36.5,
35.8, 35.6, 33.9, 33.7, 32.9, 32.9, 32.6, 32.3, 32.3, 31.9,
31.8, 31.0, 29.7, 29.2, 29.0, 28.9, 28.8, 28.6, 28.5, 28.3,
28.2, 28.1, 28.0, 27.9, 27.85, 27.8, 27.7, 27.3, 27.2, 27.1,
27.0, 26.9, 26.7, 26.4, 26.1, 26.0, 25.8, 25.5.
(40 mg, 70%). 1H NMR (400 MHz, CDCl3) d 5.31 (m, 2H),
2.37 (t, J¼7.1 Hz, 4H), 2.01 (m, 4H), 1.60 (m, 4H), 1.20–
1.37 (m, 16H). 13C NMR (100 MHz, CDCl3) d 213.0, 131.0,
42.5, 32.0, 28.9, 28.8, 28.4, 27.4, 24.1. IR: 1711 (CvO),
966 ((E)-alkene). MS (EI) m/z (rel. intensity): 250 ([Mþ],
100). Anal. (C17H30O) calcd. C 81.54, H 12.07, found C
81.66, H 12.12.
3.1.16. 17-(Triethoxysilyl)-3-oxa-bicyclo[16.3.1]docosa-
1
1(22),16,18,20-tetraen-2-one and Isomer (17). H NMR
(300 MHz, CDCl3, data of the major isomer) d 7.96 (dt,
J¼7.7, 1.5 Hz, 1H), 7.85 (t, J¼1.5 Hz, 1H), 7.50 (dt, J¼7.7,
1.5 Hz, 1H), 7.38 (t, J¼7.7 Hz, 1H), 6.44 (t, J¼7.5 Hz, 1H),
4.37 (m, 2H), 3.83 (q, J¼7.0 Hz, 6H), 2.58 (m, 2H), 1.81 (m,
2H), 1.57 (m, 4H), 1.34–1.49 (m, 14H), 1.21 (t, J¼7.0 Hz,
9H) 13C NMR (75 MHz, CDCl3, major isomer) d 167.0,
153.2, 145.3, 134.5, 132.6, 130.5, 128.1, 127.5, 127.4, 65.2,
58.5, 31.2, 28.9, 28.4, 28.3, 28.4, 28.3, 28.0, 27.9, 27.7,
27.6, 26.7, 18.1. IR (KBr) 2973, 2926, 2856, 1721, 1597,
1582, 1481, 1460, 1442, 1104, 1081, 781, 755, 726, 697,
681 cm21. MS (EI) m/z (rel. intensity): 476 [Mþ] (72), 432
(1), 431 (38), 430 (100), 412 (3), 401 (5), 385 (11), 384 (29),
291 (23), 265 (31), 255 (23), 163 (38), 135 (18), 119 (33),
107 (14), 79 (20), 55 (12). HRMS (C27H44O5Si) calcd.
476.295804, found 476.296057.
The following compounds were prepared analogously:
3.1.20. (E)-Cyclododecene (3).30 1H NMR (400 MHz,
CDCl3) d 5.37 (tt, J¼4.1, 1.0 Hz, 2H), 2.06 (q, J¼6 Hz,
4H), 1.39–1.47 (m, 4H), 1.25–1.37 (m, 9H), 1.29 (s, 3H)
13C NMR (100 MHz, CDCl3) d 131.4, 32.1, 26.3, 25.6, 25.0,
24.6.
3.1.21. 1,8-Dioxacyclotetradec-(11E)-ene-2,7-dione (6).
1
Mp¼95–96 8C. H NMR (300 MHz, CDCl3) d 5.46 (tt,
J¼3.8, 1.5 Hz, 1H), 4.14 (dd, J¼6.4, 4.5 Hz, 2H), 2.29–
2.45 (m, 4H), 1.64 (m, 2H). 13C NMR (75 MHz, CDCl3) d
173.1, 129.2, 63.1, 35.0, 31.9, 24.7. IR (KBr): 1719, 1284,
961 cm21. MS (EI) m/z (rel. intensity): 196 (1), 129 (3), 101
(3), 80 (100), 79 (14), 68 (31), 67 (16), 55 (12). Anal.
(C12H18O4) calcd. C 63.70, H 8.02, found C 63.81, H 8.09.
3.1.17. 1-(Toluene-4-sulfonyl)-11-triethoxysilylazacyclo-
henicos-(11E)-ene (20). 1H NMR (400 MHz, CDCl3) d
7.66 (d, J¼8.3 Hz, 2H), 7.28 (d, J¼8.1 Hz, 2H), 6.04 (t,
J¼7.3 Hz, 1H), 3.80 (q, J¼7.1 Hz, 6H), 3.00 (t, J¼7.1 Hz,
4H), 2.41 (s, 3H), 2.28 (m, 2H), 2.13 (m, 2H), 1.57 (m, 4H),
1.17–1.45 (m, 24H), 1.22 (t, J¼7.1 Hz, 9H) 13C NMR
(100 MHz, CDCl3) d 148.6, 142.9, 136.4, 131.9, 129.5,
127.2, 58.0, 50.2, 50.0, 37.3, 31.7, 29.8, 29.7, 29.5, 29.4,
29.3, 29.2, 29.1, 29.0, 28.9, 28.7, 28.0, 26.9, 26.5, 21.4,
18.2. IR (KAP): 3066, 3026, 2973, 2925, 2854, 1615, 1599,
1494, 1463, 1389, 1343, 1305, 1161, 1103, 1082, 958, 814,
777, 719, 653, 550 cm21. MS (EI) m/z (rel. intensity): 609
(5, [Mþ]), 565 (19), 564 (46), 563 (100), 454 (11), 163 (14).
3.1.22. 6,29-Dioxabenzo-cyclooctacos-(17E)-ene-5,30-
1
dione (9). H NMR (CDCl3, 400 MHz) d 7.71 (m, 2H),
7.52 (m, 2H), 5.32 (m, 2H), 4.28 (t, J¼6.6 Hz, 4H), 2.00 (m,
4H), 1.72 (m, 4H), 1.16–1.46 (m, 24H) 13C NMR (CDCl3,
100 MHz) d 167.7, 132.3, 130.9, 130.7, 128.9, 66.0, 32.0,
29.5, 29.3, 29.2, 28.8, 28.6, 28.0, 26.2. IR (KBr) 3067, 3025,
2925, 2853, 1730, 1600, 1465, 1448, 1288, 1126, 968,
742 cm21. MS (EI) m/z (rel. intensity): 442 [Mþ] (57), 424
(4), 294 (7), 149 (100), 124 (13), 121 (10), 96 (31), 95 (21),
82 (30), 67 (26), 55 (33), 54 (12), 43 (8), 41 (21). HRMS
(C28H42O4þNa) calcd. 465.29808, found 465.29800.
3.1.23. 1,8-Dioxacyclooctadec-(13E)-ene-2,7-dione (12).
1H NMR (400 MHz, CDCl3) d 5.35 (m, 2H), 4.07 (t,
J¼6.7 Hz, 4H), 2.31 (m, 4H), 2.01 (m, 4H), 1.55–1.66 (m,
8H), 1.40 (m, 4H) 13C NMR (100 MHz, CDCl3) d 173.2,
130.6, 64.2, 34.5, 31.6, 27.6, 25.4, 24.9. IR (KBr) 3024,
2932, 2858, 1734, 1241, 971 cm21. MS (EI) m/z (rel.
intensity): 282 [Mþ] (12), 136 (100), 121 (39), 108 (62), 79
(62), 55 (67), 29 (15). HRMS (C16H26O4þNa) calcd.
305.172879, found 305.17255.
3.1.18. 1-Benzenesulfonyl-8-triethoxysilylcyclooct-(8E)-
1
ene and Isomer (23). H NMR (300 MHz, CDCl3) d 7.88
(d, J¼7.2 Hz, 2H), 7.60 (m, 3H), 6.03 (m, 1H), 3.79 (q,
J¼7.2 Hz, 3H), 3.78 (q, J¼6.8 Hz, 3H), 2.93 (m, 1H), 2.19–
2.35 (m, 2H), 2.02–2.19 (m, 2H), 1.58–1.86 (m, 4H), 1.14–
1.54 (m, 22H), 1.21 (t, J¼7.2 Hz, 9H) 13C NMR (75 MHz,
CDCl3) d 148.6, 138.4, 138.3, 133.4, 132.2, 131.8, 129.0,
128.7, 64.1, 64.0, 58.0, 37.0, 36.6, 31.6, 31.2, 29.4, 29.2,
29.1, 28.9, 28.7, 28.6, 28.4, 28.3, 28.0, 27.8, 27.7, 27.5,
27.4, 27.1, 27.0, 26.8, 26.7, 25.9, 25.8, 25.4, 25.0, 18.2. IR
(KAP): 3062, 2972, 2926, 2854, 1616, 1586, 1480, 1460,
1446, 1389, 1304, 1145, 1103, 1083, 958, 778, 725, 692,
600 cm21. MS (EI) m/z (rel. intensity): 506 (51, [Mþ]), 261
(10), 260 (18), 259 (100), 195 (17), 163 (60), 119 (25).
3.1.24. N-Methylazacyclohexadec-(11E)-en-2-one (15).
1H NMR (400 MHz, CD2Cl2, rotamers) d 5.23 (m, 2H),
3.20 and 3.30 (m and t, J¼7.7 Hz, 2H), 2.80 and 2.90 (s,
3H), 2.20 (m, 2H), 1.92 (m, 4H), 1.00–1.60 (m, 16H) 13C
NMR (100 MHz, CD2Cl2, rotamers) d 173.3, 173.1, 131.6,
131.5, 131.3, 131.1, 51.3, 47.6, 36.0, 34.1, 33.0, 32.6, 32.5,
32.5, 31.3, 28.9, 28.7, 28.5, 28.3, 27.9, 27.5, 27.5, 27.4,
27.1, 27.0, 26.9, 26.2, 25.7. IR (KBr) 3022, 300, 2926, 2853,
1642, 968 cm21. MS (EI) m/z (rel. intensity): 251 [Mþ]
(32), 236 (2), 210 (3), 208 (4), 156 (2), 152 (3), 126 (7), 114
(8), 113 (5), 87 (12), 86 (13), 74 (9), 73 (15), 70 (39), 67
(14), 57 (11), 55 (25), 44 (100), 41 (32). HRMS (C16H29NO)
calcd. 251.224914, found 251.225135.
3.1.19. Representative procedure for the proto-desilyl-
ation reaction. (E)-Cycloheptadec-9-en-1-one (27). A
suspension of AgF (1 M in aq. MeOH, 0.47 mL,
0.47 mmol) is added to a solution of vinylsilane 26
(95 mg, 0.23 mmol) in THF (1.2 mL) and the resulting
mixture is stirred in the dark for 3h. The insoluble residues
are filtered off and are carefully washed with Et2O and
EtOAc (3 mL each), the combined filtrates are evaporated
and the residue is purified by flash chromatography
(pentane/Et2O, 8:1) to give alkene 27 as a colorless syrup
3.1.25. 3-Oxabicyclo[16.3.1]docosa-1(22),16,18,20-
1
tetraen-2-one (18). H NMR (400 MHz, CDCl3) d 8.04