K. Kira et al. / Tetrahedron 58 .2002) 1875±1888
1885
thoroughly with ethyl acetate. The ®ltrate was concentrated
in vacuo. The residue was puri®ed by silica gel column
chromatography /ether/hexane80:20) to give 35 /3.45 g,
92% in 2 steps). IR /KBr) nmax 3418, 3065, 3032, 2933,
2868, 1614, 1514, 1456, 1363, 1303, 1249, 1100, 1072,
3.1.17. Vinylsilane ,37). To a solution of the acetylene
cobalt complex 36 /589 mg, 0.746 mmol) in 75 mL of
C2H4Cl2 were added Et3SiH /2.38 mL, 14.9 mmol) and
propargyl alcohol /2.17 mL, 37.3 mmol). After stirring for
1 h at 608C, another Et3SiH /1.19 mL, 7.46 mmol) was
added. After stirring for additional 30 min at 608C, the reac-
tion mixture was ®ltered through Super-Cel and concen-
trated under reduced pressure. The residue was puri®ed by
silica gel column chromatography /ether/hexane40:60) to
1
1029, 915, 823, 752, 738, 699 cm21. H NMR /CDCl3,
300 MHz) d 1.48 /1H, q, J11.5 Hz, H-14a), 1.78±2.00
/2H, m, H-21a, 21b), 2.25 /1H, dt, J14.5, 7.5 Hz, H-8a),
2.36 /1H, dt, J11.5, 4.5 Hz, H-14b), 2.47±2.74 /3H, m,
H-8b, 17a, 17b), 3.02±3.28 /2H, m, H-12, 13), 3.15 /1H, td,
J8.5, 3.5 Hz, H-16), 3.28 /1H, dd, J9.5, 8.5 Hz, H-10),
3.35 /1H, ddd, J9.5, 7.5, 3.5 Hz, H-9), 3.43±3.76 /3H, m,
H-15, 22a, 22b), 3.59 /1H, t, J8.5 Hz, H-11), 3.78 /3H, s,
±OMe), 4.41 /1H, d, J2.0 Hz, ±OCH2C6H4OMe), 4.50
/1H, m, H-20), 4.60 /1H, d, J11.0 Hz, ±OCH2Ph), 4.75,
4.76 /total 1H, each d, J11.5 Hz, ±OCH2Php), 4.92 /1H,
d, J11.0 Hz, ±OCH2Ph), 5.02 /1H, d, J11.5 Hz,
±OCH2Php), 5.06 /1H, dm, J10.0 Hz, H-6a), 5.07 /1H,
dm, J17.0 Hz, H-6b), 5.87 /1H, dddd, J17.5, 10.5, 7.5,
6.5 Hz, H-7), 6.86 /2H, d, J9.0 Hz, aromatic), 7.21±7.40
/12H, m, aromatic). 13C NMR /CDCl3, 75 MHz) d 22.5,
36.0, 36.9, 38.1, 55.2, 61.4, 67.3, 68.9, 72.9, 73.3, 74.6,
75.2, 78.9, 79.8, 80.7, 81.7, 82.5, 82.6, 83.5, 113.9, 117.2,
127.6, 127.7, 127.9, 128.0, 128.3, 128.4, 129.3, 129.4,
129.9, 134.6, 138.3, 138.9, 159.3. Anal. Calcd for
C39H46O8: C, 72.87; H, 7.21. Found: C, 72.80; H, 7.17.
24
give the vinylsilane 37 /407 mg, 89%). [a]D 1218 /c
0.57, CHCl3). IR /KBr) nmax 3484, 3067, 3032, 2953,
2908, 2874, 2053, 2028, 1456, 1362, 1327, 1074, 1029,
1
1003, 913, 733, 698 cm21. H NMR /CDCl3, 400 MHz) d
0.63 /6Hq, J7.5 Hz, ±SiCH2CH3), 0.95 /9H, t, J7.5 Hz,
±SiCH2CH3), 1.58 /1H, q, J11.5 Hz, H-14a), 1.83 /1H,
ddt, J14.5, 6.5, 4.0 Hz, H-21a), 1.95 /1H, dddd, J14.5,
9.5, 6.5, 4.5 Hz, H-21b), 2.25 /1H, dt, J14.5, 7.5 Hz,
H-8a), 2.37 /1H, dt, J11.5, 4.0 Hz, H-14b), 2.50±2.60
/2H, m, H-8b, 17a), 2.62 /1H, dd, J14.5, 3.0 Hz, H-17b),
2.98 /1H, ddd, J11.5, 8.5, 3.0 Hz, H-16), 3.12 /1H, t,
J8.5 Hz, H-12), 3.12±3.16 /1H, m, H-13), 3.28 /1H, dd,
J9.5, 8.5 Hz, H-10), 3.37 /1H, ddd, J9.5, 7.5, 3.0 Hz,
H-9), 3.51 /1H, ddd, J11.5, 8.5, 4.5 Hz, H-15), 3.60
/1H, t, J8.5 Hz, H-11), 3.78±3.82 /2H, m, H-22a, 22b),
4.24 /1H, ddd, J9.5, 4.5, 4.0 Hz, H-20), 4.62 /1H, d, J
11.0 Hz, ±OCH2Ph), 4.75 /1H, d, J11.5 Hz, ±OCH2Php),
4.93 /1H, d, J11.0 Hz, ±OCH2Ph), 4.95 /1H, d, J
11.5 Hz, ±OCH2Php), 5.05 /1H, dm, J10.5 Hz, H-6a),
5.07 /1H, dm, J17.5 Hz, H-6b), 5.86 /1H, dddd, J17.5,
10.5, 7.5, 6.5 Hz, H-7), 6.02 /1H, dd, J4.5, 2.5 Hz, H-19),
7.26±7.38 /10H, m, aromatic). 13C NMR /CDCl3, 75 MHz)
d 2.3, 7.4, 35.9, 36.5, 37.0, 37.9, 60.9, 73.9, 75.1, 75.2, 78.9,
80.9, 82.5, 82.9, 84.2, 117.1, 127.8, 128.0, 128.2, 128.4,
128.5, 134.6, 139.4, 138.8, 141.2, 145.9. Anal. Calcd for
C37H52O6Si: C, 71.57; H, 8.44. Found: C, 71.57; H, 8.58.
3.1.16. Cyclic acetylene cobalt complex ,36). To a solution
of the diol 35 /2.45 g, 3.81 mmol) in 40 mL of CH2Cl2 was
added a solution of Co2/CO)8 /1.96 g, 5.72 mmol) in 10 mL
of CH2Cl2. After stirring for 20 min at room temperature,
BF3´OEt2 /0.97 mL, 7.62 mmol) was added at 08C. After
stirring for 15 min at room temperature, the reaction
mixture was poured into an ice-cold sat. NaHCO3 solution
and extracted with CH2Cl2 /£3). The combined extract was
washed with brine, dried over Na2SO4, and concentrated in
vacuo. The residue was puri®ed by silica gel column
chromatography /ether/hexane40:60) to give 36 /2.36 g,
3.1.18. Methylketone ,46). To a solution of the alcohol 37
/3.35 g, 5.40 mmol) in 50 mL of DMF and 10 mL of H2O
were added PdCl2 /48 mg, 0.27 mmol) and CuCl /7.6 mg,
0.54 mmol). After stirring under O2 atmosphere for 48 h at
room temperature, the reaction mixture was poured into
an ice-cold H2O and extracted with CH2Cl2 /£3). The
combined extract was washed with brine, dried over
Na2SO4, and concentrated in vacuo. The residue was puri-
®ed by silica gel column chromatography /ether/hexane
80:20) to give the methylketone 46 /2.85 g, 83%).
27
78%) as a dark red oil. [a]D 21978 /c 0.06, CHCl3). IR
/KBr) nmax 3066, 3032, 2935, 2876, 2094, 2053, 2025, 1456,
1433, 1095, 1071, 913, 735, 699, 519 cm21 1H NMR
.
/CDCl3, 400 MHz) d 1.61 /1H, q, J11.5 Hz, H-14a),
1.95 /1H, dddd, J14.5, 10.0, 7.0, 4.5 Hz, H-21a), 2.11
/1H, tdd, J10.5, 7.5, 4.0 Hz, H-21b), 2.26 /1H, dt, J
15.0, 7.5 Hz, H-8a), 2.45 /1H, ddd, J11.5, 5.5, 4.0 Hz,
H-14b), 2.57 /1H, dm, J14.5 Hz, H-8b), 2.89 /1H, dd,
J16.0, 10.5 Hz, H-17a), 3.08±3.16 /2H, m, H-12, 13),
3.30 /1H, dd, J9.5, 8.5 Hz, H-10), 3.35 /1H, ddd, J
10.5, 8.5, 4.5 Hz, H-16), 3.38 /1H, ddd, J9.5, 7.0,
3.0 Hz, H-9), 3.45±3.52 /1H, m, H-15), 3.51 /1H, dd,
J16.0, 4.5 Hz, H-17b), 3.58 /1H, t, J8.5 Hz, H-11),
3.85±3.95 /2H, m, H-22a, 22b), 4.63 /1H, d, J11.0 Hz,
±OCH2Ph), 4.69 /1H, dd, J10.0, 3.5 Hz, H-20), 4.80
/1H, d, J11.5 Hz, ±OCH2Php), 4.94 /1H, d, J11.0 Hz,
±OCH2Ph), 4.95 /1H, d, J11.5 Hz, ±OCH2Php), 5.06 /1H,
dm, J10.0 Hz, H-6a), 5.07 /1H, dm, J17.0 Hz, H-6b),
5.85 /1H, dddd, J17.5, 10.5, 7.5, 6.0 Hz, H-7), 7.26±
7.40 /10H, m, aromatic). 13C NMR /CDCl3, 100 MHz) d
36.0, 37.2, 38.7, 39.7, 60.8, 72.3, 74.9, 75.3, 77.7, 78.9,
80.8, 80.9, 81.3, 82.1, 84.2, 92.9, 101.1, 117.2, 127.5,
127.6, 127.8, 128.0, 128.3, 128.4, 134.5, 138.3, 139.0,
199.0, 199.3. ESI Q-TOF MS calcd for C37H36Co2O12Na
[M1Na]1 813.077, found 813.087.
24
[a]D 17.78 /c 1.15, CHCl3). IR /KBr) nmax 3489, 2953,
2874, 1718, 1455, 1418, 1357, 1330, 1086, 733, 699 cm21
.
1H NMR /CDCl3, 300 MHz) d 0.63 /6H, q, J8.0 Hz,
±SiCH2CH3), 0.95 /9H, t, J8.0 Hz, ±SiCH2CH3), 1.52
/1H, q, J11.5 Hz, H-14a), 1.78±2.00 /2H, m, H-21a,
21b), 2.11 /3H, s, H-6), 2.34 /1H, dt, J11.5, 4.0 Hz,
H-14b), 2.48 /1H, dd, J16.0, 8.5 Hz, H-8a), 2.54±2.61
/2H, m, H-17a, 17b), 2.69 /1H, dd, J16.0, 3.0 Hz, H-8b),
2.97 /1H, dt, J3.0, 9.0 Hz, H-16), 3.12 /1H, t, J9.0 Hz,
H-12), 3.16±3.24 /1H, m, H-13), 3.24 /1H, t, J9.0 Hz,
H-10), 3.51 /1H, ddd, J11.5, 9.0, 4.0 Hz, H-15), 3.63
/1H, t, J8.5 Hz, H-11), 3.74±3.83 /3H, m, H-9, 22a,
22b), 4.24 /1H, dt, J9.5, 4.0 Hz, H-20), 4.59 /1H, d, J
11.0 Hz, ±OCH2Ph), 4.75 /1H, d, J10.5 Hz, ±OCH2Php),
4.93 /1H, d, J11.0 Hz, ±OCH2Ph), 4.96 /1H, d, J
10.5 Hz, ±OCH2Php), 6.02 /1H, dd, J4.0, 1.5 Hz, H-19),
7.25±7.40 /10H, m, aromatic). 13C NMR /CDCl3, 75 MHz)