Tandem Michael-Intramolecular Wittig Reactions
J . Org. Chem., Vol. 66, No. 3, 2001 893
1
mp 145.5-147.5 °C; H NMR δ 0.99 (d, J ) 7 Hz, 3H), 1.55-
[(2R,3R,7R,8S)- an d (2R,3R,7S,8R)-2,3-Dim eth yl-7-ph en -
yl-1,4-d ioxa sp ir o[4.6]u n d ec-8-yl]d ip h en ylp h osp h in e Ox-
id e (6a , 6′a ). A mixture of 6a and 6′a was obtained in 92%
yield as a white solid: 1H NMR δ 1.09 (d, J ) 6 Hz, 3H), 1.21
(d, J ) 6 Hz, 3H), 1.54-1.62 (m, 1H), 1.70-1.79 (m, 1H), 1.89-
2.12 (m, 5H), 2.43 (dd, J ) 15 Hz, 10 Hz, 1H), 2.90-2.98 (m,
1H), 3.42-3.57 (m, 2H), 3.66-3.74 (m, 1H), 6.82-6.92 (m, 5H),
6.98-7.04 (m, 2H), 7.11-7.17 (m, 1H), 7.33-7.41 (m, 5H),
7.71-7.76 (m, 2H); MS (EI) m/z 460 (M+); HRMS (EI) calcd
for C29H33O3P, M, 460.2167, found, M+, 460.2161.
1.64 (m, 1H), 1.78-1.93 (m, 1H), 1.97-2.06 (m, 1H), 2.23-
2.60 (m, 6H), 3.65 (dd, J ) 13 Hz, 3 Hz, 1H), 7.48-7.55 (m,
6H), 7.82-7.88 (m, 4H); 13C NMR δ 20.55 (C6, J PC ) 6.1 Hz),
3
3
20.93 (CH3, J PC ) 12.3 Hz), 24.95 (C5), 28.05 (C3), 41.95 (C4,
1J PC ) 69.8 Hz), 44.26 (C7), 47.38 (C2, 3J PC ) 2.3 Hz), 128.72-
133.30 (aromatic carbons), 213.73 (C1); IR (KBr) 1690 cm-1 (Cd
O), 1175 cm-1 (PdO); [R]29 -0.017 (c ) 1.00, CHCl3); MS
D
(FAB) m/z 327 (M+ + 1).
tr a n s-4-(Dip h en ylp h osp h in yl)-3-isop r op ylcycloh ep -
ta n on e (5c). The reaction was performed according to the
general procedure to give 5c (1.46 g, 86%) as a white solid:
[(2R,3R,7S,8S)- a n d (2R,3R,7R,8R)-2,3,7-Tr im eth yl-1,4-
d ioxa sp ir o[4.6]u n d ec-8-yl]d ip h en ylp h osp h in e Oxid e (6b,
6′b). A mixture of 6b and 6′b was obtained in 88% yield as a
white solid: 1H NMR δ 0.80-0.93 (m, 3H), 1.12-1.27 (m, 6H),
1.40-1.50 (m, 1H), 1.69-1.87 (m, 6H), 1.92 (brd, 1H), 2.28-
2.50 (m, 2H), 3.51-3.58 (m, 2H), 7.40-7.51 (m, 6H), 7.77-
7.82 (m, 4H); MS (FAB) m/z 399 (M+ + 1); HRMS calcd for
C24H32O3P, M + 1, 399.2089, found, M+ + 1, 399.2085.
[(2R,3R,7R,8S)- a n d (2R,3R,7S,8R)-7-Isop r op yl-2,3-d i-
m eth yl-1,4-dioxaspir o [4.6]u n dec-8-yl]diph en ylph osph in e
Oxid e (6c, 6′c). A mixture of 6c and 6′c was obtained in 94%
yield as a white solid: 1H NMR δ 0.59 (d, J ) 7 Hz), 0.62 (d,
J ) 7 Hz), 0.67 (d, J ) 7 Hz), 0.69 (d, J ) 7 Hz) (total 6H),
1.19-1.27 (m, 6H), 1.32-1.95 (m, 8H), 1.99-2.10 (m, 1H),
2.34-2.65 (m, 2H), 3.50-3.63 (m, 2H), 7.40-7.55 (m, 6H),
7.78-7.90 (m, 4H); MS (FAB) m/z 427 (M+ + 1); HRMS calcd
for C26H36O3P, M + 1, 427.2402, found, M+ + 1, 427.2421.
[(2R,3R,7S,8S)- a n d (2R,3R,7R,8R)-2,3-Dim eth yl-7-p en -
tyl-1,4-d ioxa sp ir o[4.6]u n d ec-8-yl]d ip h en ylp h osp h in e Ox-
id e (6d , 6′d ). A mixture of 6d and 6′d was obtained in 96%
yield as a white solid: 1H NMR δ 0.74-1.46 (m, 17H), 1.70-
1.97 (m, 8H), 2.20-2.38 (m, 2H), 3.48-3.56 (m, 2H), 7.42-
7.48 (m, 6H), 7.77-7.84 (m, 4H); MS (FAB) m/z 455 (M+ + 1);
HRMS calcd for C28H40O3P, M + 1, 455.2715, found, M+ + 1,
455.2739.
1
mp 164.5-167.5 °C; H NMR δ 0.88 (d, J ) 7 Hz, 6H), 1.56-
1.62 (m, 1H), 1.70-1.86 (m, 2H), 2.03-2.11 (m, 1H), 2.20-
2.29 (m, 1H), 2.53-2.70 (m, 3H), 2.73-2.80 (m, 1H), 3.89 (dd,
J ) 14 Hz, 2 Hz, 1H), 7.44-7.55 (m, 6H), 7.82-7.88 (m, 4H);
13C NMR δ 20.00 (C6), 20.34, 21.22 (CH3), 25.39 (C5), 29.60
3
1
(CH, J PC ) 12.3 Hz), 37.27 (C4, J PC ) 70.5 Hz), 40.35 (C3),
43.95 (C2), 44.33 (C7), 128.74-131.66 (aromatic carbons),
214.33 (C1); IR (KBr) 1685 cm-1 (CdO), 1175 cm-1 (PdO);
[R]27 -25.60 (c ) 1.02, CHCl3); MS (FAB) m/z 355 (M+ + 1);
D
HRMS calcd for C22H28O2P, M + 1, 355.1827, found, M+ + 1,
355.1836.
t r a n s-4-(D ip h e n y lp h o s p h in y l)-3-p e n t y lc y c lo h e p -
t a n on e (5d ). The reaction was performed according to the
general procedure to give 5d (0.88 g, 48%) as a white solid:
1
mp 117.5-119.5 °C; H NMR δ 0.81 (t, J ) 7 Hz, 3H), 1.03-
1.09 (m, 2H), 1.14-1.27 (m, 5H), 1.35-1.40 (m, 1H), 1.55-
1.60 (m, 1H), 1.73-1.88 (m, 1H), 2.02-2.11 (m, 1H), 2.15-
2.39 (m, 3H), 2.46-2.64 (m, 3H), 3.78 (dd, J ) 13 Hz, 3 Hz,
1H), 7.46-7.52 (m, 6H), 7.82-7.88 (m, 4H); 13C NMR δ 13.97
3
(CH3), 20.17 (C6, J PC ) 5.4 Hz), 22.42, 26.61, 31.28 (CH2),
3
24.97 (C5), 32.76 (C3), 33.86 (CH2, J PC ) 11.5 Hz), 39.71 (C4,
1J PC ) 69.8 Hz), 44.37 (C7), 45.44 (C2), 128.72-133.21 (aro-
matic carbons), 213.91 (C1); IR (KBr) 1685 cm-1 (CdO), 1170
cm-1 (PdO); [R]27 -9.60 (c ) 1.02, CHCl3); MS (FAB) m/ s
D
Ack n ow led gm en t. This work was supported by a
Grant-in-Aid for Scientific Research from the Ministry
of Education, Science, and Culture of J apan (No
11650889). We are grateful to the Ihara Chemical Co.,
Ltd., for the gift of triphenylphosphine. We thank
Welfide Co., Ltd., and Kissei Pharmaceutical Co., Ltd.,
for the MS and HRMS measurements.
383 (M+ + 1); HRMS calcd for C24H32O2P, M + 1, 383.2140,
found, M+ + 1, 383.2158.
Gen er a l P r oced u r e for th e Rea ction of th e Keton es
5a -d w ith (R,R)-(-)-2, 3-Bu ta n ed iol. A solution of (R,R)-
(-)-2,3-butanediol (14 mg, 0.16 mmol), a catalytic amount of
p-toluenesulfonic acid monohydrate, and the ketone (0.08
mmol) in dry toluene (3 mL) was refluxed for 16 h using the
Dean-Stark apparatus. After being cooled to room tempera-
ture, the mixture was poured into an aqueous 10% NaOH
solution and the resulting solution was extracted with CH2-
Cl2. The combined organic layer was washed with water and
brine, dried over Na2SO4, and concentrated under reduced
pressure. After the measurement of 31P NMR, the crude
product was purified by flash column chromatography on silica
gel using AcOEt as the eluent.
Su p p or tin g In for m a tion Ava ila ble: A modified proce-
dure for synthesis of phosphonium salt 1, 1H, 13C, and 31P NMR
1
spectra for compounds 5a -d , H and 31P NMR spectra for a
mixture of diastereomers 6a -d and 6′a -d , and X-ray crystal-
lographic data for 6a . This material is available free of charge
J O001379A