Rhodium(I)-Catalyzed Enantioselective Ring-Opening and Isomerization of Cyclobutanols through a (Z)-Unsaturated Ketone Intermediate

摘要

A rhodium(I)-catalyzedhighly enantioselective ring-opening andisomerization of cyclobutanols has been developed. The reaction providesa mild, atom-economical, and redox-neutral approach for the synthesisof chiral acyclic ketones bearing a & beta;-tertiary stereocenter.Excellent enantioselectivities and high yields can be achieved usingcyclobutanols with alkoxy substituents at the C3 position. Mechanisticstudies reveal that cyclobutanol only undergoes intramolecular hydrogenmigration, and the formation of a (Z)-unsaturatedketone intermediate is crucial for achieving high enantioselectivity.

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