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Highly Enantioselective Reductive Cyclization of Acetylenic Aldehydes via Rhodium Catalyzed Asymmetric Hydrogenation

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Jong Uk Rhee and Michael J. Krische*

University of Texas at Austin, Department of Chemistry and Biochemistry, Austin, Texas 78712

J. Am. Chem. Soc., 2006, 128 (33), pp 10674–10675

DOI: 10.1021/ja0637954

Publication Date (Web): August 1, 2006

Abstract

Catalytic hydrogenation of acetylenic aldehydes 1a−12a using chirally modified cationic rhodium catalysts enables highly enantioselective reductive cyclization to afford cyclic allylic alcohols 1b−12b. Using an achiral hydrogenation catalyst, the chiral racemic acetylenic aldehydes 13a−15a engage in highly syn-diastereoselective reductive cyclizations to afford cyclic allylic alcohols 13b−15b. Ozonolysis of cyclization products 7b and 9b allows access to optically enriched α-hydroxy ketones 7c and 9c. Reductive cyclization of enyne 7a under a deuterium atmosphere provides the monodeuterated product deuterio-7b, consistent with a catalytic mechanism involving alkyne−carbonyl oxidative coupling followed by hydrogenolytic cleavage of the resulting oxametallacycle. These hydrogen-mediated transformations represent the first examples of the enantioselective reductive cyclization of acetylenic aldehydes.

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Published In Issue August 23, 2006
Received May 30, 2006

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Communication

Highly Enantioselective Reductive Cyclization of Acetylenic Aldehydes via Rhodium Catalyzed Asymmetric Hydrogenation

Abstract

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History

Recommend & Share

Related Content

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Highly Enantioselective Direct Reductive Coupling of Conjugated Alkynes and α-Ketoesters via Rhodium-Catalyzed Asymmetric Hydrogenation

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