Catalytic Asymmetric Reactions for Organic Synthesis:  The Combined C−H Activation/Siloxy-Cope Rearrangement

Tetrakis(N-[4-dodecylbenzenesulfonyl]-(l)-prolinate) dirhodium [Rh2(S-DOSP)4]-catalyzed decomposition of vinyldiazoacetates in the presence of allyl silyl ethers results in the formation of the direct C−H insertion product and the product derived from a combined C−H activation/siloxy-Cope rearrangem...

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Bibliographic Details
Published in:Journal of organic chemistry 2004-12, Vol.69 (26), p.9241-9247
Main Authors: Davies, Huw M. L, Beckwith, Rohan E. J
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
Kinetics and mechanisms
Organic chemistry
Reactivity and mechanisms
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Summary:Tetrakis(N-[4-dodecylbenzenesulfonyl]-(l)-prolinate) dirhodium [Rh2(S-DOSP)4]-catalyzed decomposition of vinyldiazoacetates in the presence of allyl silyl ethers results in the formation of the direct C−H insertion product and the product derived from a combined C−H activation/siloxy-Cope rearrangement. Both products are formed with very high diastereoselectivity (>94% de) and high enantioselectvity (78−93% ee). Under thermal or microwave conditions, the direct C−H insertion product undergoes a siloxy-Cope rearrangement in a stereoselective manner.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo048429m