G. Blay et al. / Tetrahedron Letters 44 (2003) 8117–8119
8119
position of the epoxide and TMS groups. Thus, methyl
migration is found when both groups are on the same
ring, while methylene migration is preferred if they are
placed on different rings. The TMS group also inhibits
the Grob-type fragmentation of the rearranged prod-
ucts and determines the location of the new double
bond in the final products.
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Acknowledgements
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Financial support from the European Commission
(FAIR CT96-1781) is gratefully acknowledged. A.M.C.
thanks the European Commission for a pre-doctoral
grant.
12. Blay, G.; Cardona, L.; Garc´ıa, B.; Pedro, J. R. J. Org.
Chem. 1993, 58, 7204–7208.
13. Compound 11: [h]D25=+24.1 (c 0.73, CHCl3); MS (EI)
m/z 166 (M+, 10), 149 (9), 148 (70), 136 (26), 122 (100),
107 (62), 93 (43); HRMS: 166.1363 (M+), C11H18O
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1H NMR (300 MHz, CDCl3) l 5.31 (1H, br s), 3.57 (1H,
dd, J=2.1; 6.6 Hz), 2.17–1.87 (2H, m), 1.85–1.40 (10H,
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121.0 (d), 74.0 (d), 50.6 (s), 37.1 (t), 32.6 (t), 27.5 (t), 27.0
(t), 26.9 (t), 21.7 (t), 19.6 (q).
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14. Compound 10: [h]2D5=−125.8 (c 0.30, CHCl3); MS (EI)
m/z 149 (M+−17, 10), 148 (82), 122 (100), 107 (50), 93
(53), 79 (42), 71 (42), 57 (75) 55 (56); HRMS: 149.1321
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2.20–1.80 (4H, m), 1.75–1.30 (6H, m), 1.40–1.05 (2H, m),
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m), 1.95–1.85 (3H, m), 1.79–1.68 (3H, m), 1.65–1.30 (5H,
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121.9 (d), 79.1 (d), 40.2 (s), 35.9 (t), 31.6 (t), 30.7 (t), 25.7
(t), 25.0 (t), 18.6 (t), 17.2 (q).
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