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- Title
Angular Alkylation of cis-Decalin Epoxides with C-nucleophiles: Mechanism, scope, and limitations of a novel bridgehead functionalisation.
- Authors
Huber, Udo; Boland, Wilhelm
- Abstract
The angular alkylation of cis-decalin epoxides like 5 or 7 can be achieved at C(8a) in good yield by using CuI and a large excess of Grignard reagents without an sp3 centre at C(2). The reaction proceeds via a carbenium-ion intermediate which is stabilised by homoconjugative interaction with the adjacent double bond. Due to 1,3-diaxial strain in the alkoxides resulting from alkylation or reduction at C(4a) of the epoxides 5 or 7, the nucleophile is delivered selectively to C(8a). Grignard reagents possessing H-atoms at C(β), transfer a hydride to the epoxide yielding the trans-decalol 11 ( Grignard reduction). The angular alkylation of 5 with allylic and benzylic Grignard reagents proceeds with good yield.
- Publication
Helvetica Chimica Acta, 1995, Vol 78, Issue 1, p87
- ISSN
0018-019X
- Publication type
Article
- DOI
10.1002/hlca.19950780109