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Synfacts 2013; 9(1): 0067
DOI: 10.1055/s-0032-1317772
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

In Situ Aldehyde Enolate Formation by Rhodium-Catalyzed Isomerization

Contributor(s):
Hisashi Yamamoto
,
Patrick Brady
Lin L, Yamamoto K, Matsunaga S, * Kanai M. * The University of Tokyo and ERATO Japan Science and Technology Agency, Tokyo, Japan
Rhodium-Catalyzed Cross-Aldol Reaction: In Situ Aldehyde-Enolate Formation from Allyloxyboranes and Primary Allylic Alcohols.

Angew. Chem. Int. Ed. 2012;
51: 10275-10279
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Publication History

Publication Date:
17 December 2012 (online)

 
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Key words

rhodium - aldol reaction - aldehydes - allylic alcohols - allyloxyboranes

Significance

Aldol reactions in which the aldol donor is derived from an aldehyde, are particularly challenging. This report describes a strategy in which aldehyde enolates are generated in situ by rhodium-catalyzed isomerization of triallylboroxanes. High syn-selectivity is obtained for a variety of aldehyde-donor and -acceptor partners.


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Comment

Remarkably, the use of triallyloxyboranes is not required; simple primary and secondary allylic alcohols also undergo the isomerization–cross-aldol sequence with similar levels of reactivity and selectivity, presumably through a rhodium-enolate or -enol mechanism.


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