OCH), 3.84–3.71 (2H, m, CHHO and OCHH), 3.49–3.37 (2H,
m, CHHO and OCHH), 2.20 (2H, t, J 7.2, CH C᎐CH ), 1.77–
26.2 (CH2), 26.0 (CH2), 21.3 (CH2); selected signal for the
minor isomer: 3.99 (1H minor isomer, dd, J 12.3 and 3.2, ax-
CHHOCH); further signals for the minor isomer could not be
resolved, and the stereochemistry could not be determined;
m/z (CI) 235 (100%, MNaϩ). Found (CI): MNaϩ 235.1674.
C13H24O2Naϩ requires 235.1674.
᎐
2
2
1.46 (8H, m, 4 × CH2), Ϫ0.04 (9H, s, Si(CH3)3); δC (50 MHz;
CDCl ): 144.3 (C᎐CH ), 108.2 (C᎐CH ), 98.5 (CH), 66.2 (CH ),
᎐
᎐
3
2
2
2
62.0 (CH2), 38.1 (CH2), 30.6 (CH2), 27.1 (CH2), 25.4 (CH2),
19.4 (CH2), Ϫ1.52 (SiCH3); m/z (CI) 243 (100%, MHϩ). Found
(CI): MHϩ 243.1780. C13H26O2SiHϩ requires 243.1780.
3-(3Ј-Methyloctahydroisochromen-1Ј-yl)butan-1-ol 22
4-(4Ј-Methyltetrahydropyran-2Ј-yl)butan-1-ols cis-20 and
trans-20
To a stirred solution of 14–16 (20 mg, 0.09 mmol) in methanol
at ambient temperature was added palladium on carbon (6 mg,
30% by weight). The reaction mixture was degassed before
being placed under an atmosphere of hydrogen gas, and stirred
at ambient temperature for 2 hours. The mixture was filtered
through Celite and concentrated in vacuo to leave a colourless
oil. Purification by flash column chromatography, eluting with
50% ethyl acetate–40/60 petroleum ether, gave 22 (20 mg, 99%)
as a colourless oil. νmax (thin film)/cmϪ1 3405 (br, O–H), 2919,
2854, 1057, 1029 (C–O); δH (600 MHz; CDCl3): 3.63 (2H, t,
J 5.9, CH2OH), 3.46 (1H, dqd, J 12.3, 6.2 and 1.8, CH3CH),
2.97 (1H, td, J 8.9 and 2.6, CH3CHOCH), 1.84–1.15 (14H, m,
CHH, CH and 6 × CH2), 1.14 (3H, d, J 6.2, CH3), 0.97–0.76
(4H, m, CH and 3 × CHH); δC (150 MHz; CDCl3): 81.4
(OCHCH2), 73.4 (CH3CHO), 62.8 (CH2OH), 46.0 (CH), 41.1
(CH), 41.2 (CH2), 33.3 (CH2), 32.7 (CH2), 31.9 (CH2), 27.7
(CH2), 26.3 (CH2), 20.1 (CH2), 22.0 (CH3), 21.4 (CH2); m/z (CI)
227 (100%, MHϩ). Found (CI): MHϩ 227.2015. C14H26O2Hϩ
requires 227.2011.
From 2, 3 and 4. To a stirred solution of a 52:31:13 mixture
of the alkenes 2, 3, 4 (100 mg, 0.6 mmol) in methanol (10 mL) at
ambient temperature was added palladium on carbon (30 mg,
30% by weight). The reaction mixture was degassed before
being placed under an atmosphere of hydrogen gas, and stirred
at ambient temperature for 24 hours. The mixture was filtered
through Celite and concentrated in vacuo to leave only cis- and
trans-20 as a colourless oil, in a 30:1 ratio of cis:trans by inte-
gration of the CH3 doublets at δH = 0.92 (cis) and 0.90 (trans) in
the 600 MHz proton NMR spectrum, (100 mg, 100%). Flash
column chromatography, eluting with 50% ethyl acetate–40/60
petroleum ether, isolated cis-20 as a colourless oil (the trace
of trans-20 could not be detected). νmax (thin film)/cmϪ1 3392
(br, O–H), 2921, 1634 (C᎐C), 1098, 1066 (C–O); δ (600
᎐
H
MHz; CDCl3): 3.97 (1H, dd, J 11.4 and 3.5, eq-CHHO), 3.64
(2H, t, J 6.5, CH2OH), 3.38 (1H, td, J 11.4 and 2.1, ax-CHHO),
3.22 (1H, m, OCH), 1.66–1.39 (9H, m, CHCH3, CHH,
eq-CHHCH2O and 3 × CH2), 1.18 (1H, qd, J 12.5, 4.6,
ax-CHHCH2O), 0.92 (3H, d, J 6.3, CH3), 0.90–0.86 (1H, m,
CHH); δC (150 MHz; CDCl3): 77.4 (OCH), 68.0 (CH2O),
62.8 (CH2OH), 40.6 (CH2), 36.0 (CH2), 34.7 (CH2CH2O),
32.7 (CH2CH2OH), 30.3 (CH3CH), 22.3 (CH3), 21.6
(OCHCH2CH2); m/z (CI) 173 (100%, MHϩ). Found (CI):
MHϩ 173.1542. C10H20O2Hϩ requires 173.1542. Selected signal
for trans-20: δH (600 MHz; CDCl3): 0.90 (3H, d, J 6.1, CH3).
Further signals for the trans isomer could not be resolved.
Acknowledgements
We thank the EPSRC (to E. W. T. and D. J. D.), the Novartis
Research Fellowship (to S. V. L.) and Pfizer inc., Groton,
USA for financial support.
References
1 For examples see: (a) D. E. Levy and C. Tang, The Chemistry of
C-Glycosides, Pergamon, Oxford, 1995; (b) M. H. D. Postema,
Tetrahedron, 1992, 48, 8545.
From 4. To a stirred solution of alkene 4 (5.0 mg, 0.03 mmol)
in methanol (1 mL) at ambient temperature was added pal-
ladium on carbon (1 mg, 20% by weight). The reaction mixture
was degassed before being placed under an atmosphere of
hydrogen gas, and stirred at ambient temperature for 2 hours.
The mixture was filtered through Celite and concentrated in
vacuo to leave cis- and trans-20 as a colourless oil, as a 5:1
(cis:trans) mixture of diastereoisomers by integration of the
CH3 doublets at δH = 0.90 (minor) and 0.92 (major) in the 600
MHz proton NMR spectrum, (4.9 mg, 98%).
2 Preceding paper: M. F. Buffet, D. J. Dixon, G. L. Edwards, S. V. Ley
and E. W. Tate, J. Chem. Soc., Perkin Trans. 1, 2000, DOI: 10.1039/
a909300a. For other studies on anomeric oxygen to carbon
rearrangements see also: (a) M. F. Buffet, D. J. Dixon, G. L.
Edwards, S. V. Ley and E. W. Tate, Synlett, 1997, 1055; (b) M. F.
Buffet, D. J. Dixon, S. V. Ley and E. W. Tate, Synlett, 1998, 1091; (c)
D. J. Dixon, S. V. Ley and E. W. Tate, Synlett, 1998, 1093; (d) D. J.
Dixon, S. V. Ley and E. W. Tate, J. Chem. Soc., Perkin Trans. 1, 1998,
3125; (e) D. J. Dixon, S. V. Ley and E. W. Tate, J. Chem. Soc., Perkin
Trans. 1, 1999, 2665.
3 For a review see: B. B. Snider in Comprehensive Organic Synthesis,
ed. B. M. Trost and I. Fleming, Pergamon Press, New York, 1991,
Vol. 2, pp. 527–561.
4 For examples see: (a) E. Hanschke, Chem. Ber., 1955, 88, 1053;
(b) L. Coppi, A. Ricci and M. Taddei, J. Org. Chem., 1988, 53, 911;
(c) W. C. Zhang, G. S. Viswanathan and C. J. Li, Chem. Commun.,
1999, 291; (d) M. Nishizawa, T. Shigaraki, H. Takao, H. Imagawa
and A. Sugihara, Tetrahedron Lett., 1999, 40, 1153.
5 For examples see: (a) M. L. Melany, G. A. Lock and D. W.
Thompson, J. Org. Chem., 1985, 50, 3925; (b) J.-X. Wang and
H. Alper, J. Org. Chem., 1986, 51, 275; (c) Y. Hu, D. J. Skalitzky
and S. D. Rychnovsky, Tetrahedron Lett., 1996, 37, 8679. See also:
(d) W. H. Bunnelle, D. W. Seamon, D. L. Mohler, T. F. Ball and
D. W. Thompson, Tetrahedron Lett., 1984, 25, 2653; (e) A.
Castañeda, D. J. Kucera and L. E. Overman, J. Org. Chem., 1989,
54, 5695 and references cited therein; (f) N. A. Nikolic, E. Gonda,
C. P. Desmond Longford, N. T. Lane and D. W. Thompson, J. Org.
Chem., 1989, 54, 2748; (g) S. D. Rychnovsky, Y. Q. Hu and
B. Ellsworth, Tetrahedron Lett., 1998, 39, 7271.
6 For examples see: (a) P. R. Stapp, J. Org. Chem., 1969, 34, 479;
(b) L. Coppi, A. Ricci and M. Taddei, Tetrahedron Lett., 1987, 28,
973; (c) Z. Y. Wei, J. S. Li, D. Wang and T. H. Chan, Tetrahedron
Lett., 1987, 28, 3441; (d) I. E. Markó and F. Chellé, Tetrahedron
Lett., 1997, 38, 2895; (e) J. Yang, G. S. Viswanathan and C. J. Li,
Tetrahedron Lett., 1999, 40, 1627; (f) G. S. Viswanathan, J. Yang
and C. J. Li, Org. Lett., 1999, 1, 993.
3-(Octahydroisochromen-1Ј-yl)butan-1-ol 21
To a stirred solution of 11–13 (34 mg, 0.16 mmol) in methanol
(4 mL) at ambient temperature was added palladium on carbon
(7 mg, 20% by weight). The reaction mixture was degassed
before it was placed under an atmosphere of hydrogen gas, and
stirred at ambient temperature for 24 hours. The mixture was
filtered through Celite and concentrated in vacuo to leave a
colourless oil. Purification by flash column chromatography,
eluting with 50% ethyl acetate–40/60 petroleum ether, gave 21,
as the major component in an inseparable 10:1 mixture of two
isomers by integration of the signals at δH = 3.99 (minor isomer)
and 3.95 (21) in the 600 MHz proton NMR spectrum and by
GC analysis (2 peaks, retention times: 18.88, 19.65 minutes,
ratio 10:1) (32 mg, 93%) as a colourless oil. νmax (thin film)/
cmϪ1 3406 (br, O–H), 2920, 2852, 1079, 1055 (C–O); δH (600
MHz; CDCl3): 3.95 (1H, dd, J 10.8 and 4.5, eq-CHHOCH),
3.61 (2H, t, J 5.5, CH2OH), 3.43 (1H, td, J 10.8 and 2.1,
ax-CHHOCH), 2.93 (1H, br t, J 8.1, OCH), 1.96–0.77 (18H, m,
CHCHCHO, CHCHO and 8 × CH2); δC (150 MHz; CDCl3):
81.5 (OCH), 68.1 (CH2), 62.7 (CH2), 46.4 (CH), 41.0 (CH),
33.8 (CH2), 33.3 (CH2), 32.8 (CH2), 32.1 (CH2), 27.7 (CH2),
J. Chem. Soc., Perkin Trans. 1, 2000, 1829–1836
1835