Recent developments of direct rhenium-catalyzed [1,3]-transpositions of allylic alcohols and their silyl ethers

The direct metal-catalyzed [1,3]-transposition of allylic alcohols and allylic silyl ethers is a synthetically useful isomerization process that occurs via [3,3]-sigmatropic rearrangement induced by high oxidation state oxometal complexes. The isomerization requires only a catalytic amount of promot...

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Bibliographic Details
Published in:Chemical Society reviews 2014-07, Vol.43 (13), p.4381-4394
Main Authors: Volchkov, Ivan, Lee, Daesung
Format: Article
Language:English
Subjects:
Alcohols
Ethers
Isomerization
Stereoselectivity
Synthesis
Valence
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Summary:The direct metal-catalyzed [1,3]-transposition of allylic alcohols and allylic silyl ethers is a synthetically useful isomerization process that occurs via [3,3]-sigmatropic rearrangement induced by high oxidation state oxometal complexes. The isomerization requires only a catalytic amount of promoter, and high chirality transfer can be achieved. Thus, it bears a significant potential to become a powerful tool in multistep synthesis. Although [1,3]-transposition of allylic alcohols has been known since the late 1960s, the development of synthetically useful protocols that allow for a high level of regio- and stereoselectivity control and their synthetic applications have emerged only recently. This tutorial review summarizes recently developed regioselective [1,3]-transpositions of allylic alcohols and silyl ethers and their applications to natural product synthesis. This tutorial review describes recent developments of various allylic transposition strategies involving rhenium-catalyzed rearrangement followed by regio- and stereostereoselective trapping processes and their applications to natural product synthesis.
ISSN:0306-0012
1460-4744
DOI:10.1039/c4cs00036f