C. Mukai et al. / Tetrahedron 58 *2002) 2755±2762
2761
(2H, t, J6.4 Hz), 3.61 (2H, t, J6.4 Hz), 2.09 (2H, t, J
7.3 Hz), 2.04 (2H, t, J7.8Hz), 1.71 (2H, tt, J7.3, 6.4 Hz),
1.55±1.43 (4H, m), 0.89 (9H, s), 0.05 (6H, s); 13C NMR d
159.0, 149.0, 130.7, 129.1, 113.7, 108.9, 72.5, 69.7, 62.9,
55.1, 35.7, 32.4, 32.4, 27.8, 25.9, 23.9, 18.3, 25.4; FABMS
m/z 273 (M111, 12). FABHRMS calcd for C15H33O2Si
273.2250, found 273.2256.
28 (2.00 g, 7.18mmol). Compound 29 was a colorless oil:
IR 3402, 1646 cm21; 1H NMR d 7.44±7.24 (7H, m), 6.90±
6.85 (2H, m), 4.75 (2H, s), 4.60 (1H, dd, J11.9, 6.3 Hz),
4.42 (2H, s), 3.80 (3H, s), 3.45 (2H, t, J6.3 Hz), 2.10 (4H,
t, J7.6 Hz), 1.86±1.61 (6H, m); 13C NMR d 159.0, 148.6,
131.6, 130.5, 129.1, 128.2, 128.1, 122.6, 113.7, 109.3, 90.2,
84.7, 72.4, 69.6, 62.6, 55.1, 37.3, 35.5, 32.3, 27.7, 23.1; MS
m/z 378(M 1, 0.9). Anal. Calcd for C25H30O3: C, 79.33; H,
7.99. Found: C, 79.49; H, 8.26.
1.2.12.
10-'tert-Butyldimethylsiloxy)-6-methylene-1-
phenyldec-1-yn-3-ol '25). According to the procedure
described for the preparation of 9, 25 (5.20 g, 55%) was
obtained from 24 (6.95 g, 25.5 mmol). Compound 25 was
a colorless oil: IR 3453, 1684 cm21; 1H NMR d 7.44±7.29
(5H, m), 4.81 (1H, s), 4.78 (1H, s), 4.62 (1H, t, J6.4 Hz),
3.62 (2H, t, J6.4 Hz), 2.26 (2H, t, J7.8Hz), 2.07 (2H, t,
J7.3 Hz), 1.97±1.92 (2H, m), 1.55±1.48(4H, m), 0.90
(9H, s), 0.05 (6H, s); 13C NMR d 148.8, 131.6, 128.4,
128.2, 122.6, 109.5, 89.9, 85.1, 63.0, 62.6, 35.9, 35.8,
32.5, 31.5, 26.0, 23.9, 18.3, 25.3; MS m/z 372 (M1, 0.5).
Anal. Calcd for C23H36O2Si: C, 74.14; H, 9.74. Found: C,
73.84; H, 10.01.
1.2.17. 3-Acetoxy-7-methylene-1-phenyldec-1-yn-10-ol
'30). According to the procedure described for acetylation
and debenzylation (25 to 26 and 23 to 24), 30 (635 mg,
80%) was obtained from 29 (1.00 g, 2.64 mmol). Com-
pound 30 was a colorless oil: IR 3444, 1733, 1644 cm21
;
1H NMR d 7.47±7.43 (5H, m), 5.62 (1H, t, J6.4 Hz), 4.79
(1H, s), 4.78(1H, s), 3.68±3.64 (2H, m), 2.12±2.10 (4H, m),
2.11 (3H, s), 1.88±1.60 (6H, m); 13C NMR d 170.0, 148.4,
131.8, 128.5, 128.2, 122.2, 109.7, 86.4, 85.3, 64.3, 62.5,
35.3, 34.3, 32.0, 30.6, 22.9, 21.0; MS m/z 300 (M1, 8.7).
Anal. Calcd for C19H24O3: C, 75.97; H, 8.05. Found: C,
75.68; H, 8.19.
1.2.13. 3-Acetoxy-6-methylene-1-phenyldec-1-yn-10-ol
'26). According to the procedure described for the prepa-
ration of 12, 26 (52.2 mg, 57%) was obtained from 25
(112 mg, 0.29 mmol). Compound 26 was a colorless oil:
1.2.18. Hexacarbonyl-m-[h4-3-acetoxy-7-methylene-1-
phenyldec-1-yn-10-ol]dicobalt'Co±Co) '31). According
to the procedure described for the preparation of 12, 31
(139 mg, 88%) was obtained from 30 (80.7 mg, 0.27
mmol). Compound 31 was a reddish brown oil: IR 2093,
2056, 2025, 1732 cm21; 1H NMR d 7.48±7.31 (5H, m), 6.40
(1H, dd, J7.8, 5.3 Hz), 4.79 (1H, s), 4.70 (1H, s), 3.65±
3.61 (2H, m), 2.14 (3H, s), 2.09±2.03 (4H, m), 1.87±1.57
(6H, m); 13C NMR d 198.9, 170.6, 148.3, 137.4, 129.4,
128.9, 127.9, 109.9, 96.4, 90.5, 73.9, 62.7, 37.1, 35.3,
32.0, 30.7, 24.1, 20.7; MS m/z 530 (M1256, 0.8). Anal.
Calcd for C25H24Co2O9: C, 51.21; H, 4.13. Found: C,
50.93; H, 4.19.
1
IR 3460, 1734 cm21; H NMR d 7.45±7.28(5H, m), 5.60
(1H, t, J6.8Hz), 4.76 (1H, s), 4.75 (1H, s), 3.66 (2H, t,
J6.8Hz), 2.12±2.05 (4H, m), 2.11 (3H, s), 1.89±1.45 (6H,
m); 13C NMR d 170.0, 147.8, 131.8, 128.6, 128.2, 122.2,
109.9, 86.3, 85.5, 64.2, 62.8, 35.7, 33.0, 32.4, 31.3, 23.8,
21.0; MS m/z 300 (M1, 5.2). HRMS calcd for C19H24O3
300.1725, found 300.1730.
1.2.14. Hexacarbonyl-m-[h4-3-acetoxy-6-methylene-1-
phenyldec-1-yn-10-ol]dicobalt'Co±Co) '27). According
to the procedure described for the preparation of 12, 27
(271 mg, 92%) was obtained from 26 (150 mg, 0.50
mmol). Compound 27 was a reddish brown oil: IR 2093,
2056, 2025, 1734 cm21; 1H NMR d 7.48±7.28(5H, m), 6.39
(1H, t, J6.3 Hz), 4.78(1H, s), 4.72 (1H, s), 3.66±3.60 (2H,
m), 2.19±1.94 (6H, m), 2.13 (3H, s), 1.62±1.37 (4H, m); 13C
NMR d 198.8, 170.5, 147.7, 137.4, 129.4, 128.9, 127.9,
109.8, 96.3, 90.5, 73.8, 62.7, 35.9, 35.5, 32.3, 32.2, 23.8,
20.7; MS m/z 586 (M1, 3.3). Anal. Calcd for C25H24Co2O9:
C, 51.21; H, 4.13. Found: C, 51.06; H, 4.21.
1.2.19. Hexacarbonyl-m-[h4-'6Rp,8Sp)-8-phenylethynyl-
1-oxaspiro[5.5]-undecane]dicobalt'Co±Co) '32a).
A
reddish brown oil: IR 2087, 2050, 2023 cm21; H NMR d
7.54±7.26 (5H, m), 3.73±3.59 (2H, m), 3.31 (1H, tt, J
11.9, 3.3 Hz), 2.48±2.43 (1H, m), 2.14±1.98 (2H, m),
1.91±1.09 (11H, m); 13C NMR d 200.0, 138.4, 129.2,
128.8, 127.5, 106.5, 91.5, 71.9, 60.8, 42.2, 37.0, 36.4,
35.3, 34.8, 26.1, 21.0, 18.9; FABMS m/z 541 (M111,
0.8). FABHRMS calcd for C24H23Co2O7 541.0108, found
541.0089.
1
1.2.15. 1-'4-Methoxyphenyloxy)-4-methyleneoctan-8-ol
'28). According to the procedure described for the prepa-
ration of 10, 28 (5.44 g, 98%) was obtained from 23 (7.85 g,
20.0 mmol). Compound 28 was a colorless oil: IR 3421,
1.2.20. Hexacarbonyl-m-[h4-'6Rp,8Rp)-8-phenylethynyl-
1-oxaspiro[5.5]-undecane]dicobalt'Co±Co) '32b).
A
reddish brown oil: IR 2089, 2050, 2023 cm21; H NMR d
7.52±7.30 (5H, m), 3.74±3.70 (2H, m), 3.03 (1H, tt, J
11.9, 3.3 Hz), 2.40 (1H, m), 2.12±2.03 (2H, m), 1.88±
1.25 (11H, m); 13C NMR d 199.7, 138.3, 129.2, 128.8,
127.6, 10.5.1, 91.1, 73.1, 61.2, 44.4, 38.5, 35.4, 35.2, 31.4,
26.2, 22.6, 19.1; FABMS m/z 541 (M111, 0.7). FABHRMS
calcd for C24H23Co2O7 541.0108, found 541.0140.
1
1645 cm21 1H NMR d 7.28±7.25 (2H, m), 6.89±6.86
;
(2H, m), 4.72 (2H, s), 4.43 (2H, s), 3.80 (3H, s), 3.65 (2H,
t, J6.4 Hz), 3.45 (2H, t, J6.4 Hz), 2.08(2H, t, J7.8Hz),
2.04 (2H, t, J7.3 Hz), 1.77±1.71 (2H, m), 1.59±1.46 (4H,
m); 13C NMR d 159.0, 158.9, 148.9, 130.6, 129.2, 113.7,
109.1, 72.5, 69.7, 62.6, 55.2, 35.7, 32.3, 27.8, 23.8; MS m/z
278(M 1, 9.9). Anal. Calcd for C17H26O3: C, 73.34; H, 9.41.
Found: C, 72.97; H, 9.69.
1.2.21. Hexacarbonyl-m-[h4-'2Rp,5Sp)-2-phenylethynyl-
6-oxaspiro[4.5]-decane]dicobalt'Co±Co) '33a). A reddish
brown oil: IR 2087, 2050, 2023 cm21; 1H NMR d 7.56±7.30
(5H, m), 3.74±3.45 (3H, m), 2.29 (1H, m), 2.20±2.02 (2H,
m), 1.98±1.80 (2H, m), 1.73±1.43 (7H, m); 13C NMR 199.8,
1.2.16. 10-'4-Methoxyphenyloxy)-7-methylene-1-phenyl-
dec-1-yn-3-ol '29). According to the procedure described
for the preparation of 9, 29 (2.29 g, 84%) was obtained from