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Synfacts 2005(0): 0054-0054  
DOI: 10.1055/s-2005-869936
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Allylation of Aldehydes Catalyzed by a Chiral Indium(III)-BINOL Complex

Contributor(s): Mark Lautens, Y. Eric Fang
Y.-C Teo, K.-T. Tan, T.-P. Loh*
National Univerity of Singapore, Singapore
Catalytic Asymmetric Allylation of Aldehydes via a Chiral Indium(III) Complex
Chem. Commun.  2005,  1318-1320  
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Publication History

Publication Date:
20 July 2005 (online)

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Key words

asymmetric catalysis - allylation - trialkylallyl­-stannanes - indium - aldehydes - homoallylic alcohols

Significance

The first chiral indium(III)-catalyzed allylation reaction of aldehydes is disclosed. By using catalytic InCl3/(S)-BINOL, highly enantioselective formation of homoallylic alcohols was achieved using allyltributylstannane.

Comments

This allylation protocol developed is relatively simple, mild and affords excellent enan­tioselectivity with both aromatic and aliphatic aldehydes. The most likely drawback is the high toxicity of organotin reagents. Further studies to determine the scope of the reaction with a variety of aromatic aldehydes is required. Preliminary mechanistic studies revealed that the active chiral Lewis acid catalyst is a BINOL-In(III)-allyl complex. There are many asymmetric allylation reagents or allylation catalysts present in the literature (for a review see: S. E. Denmark, J. Fu Chem. Rev. 2003, 103, 2763-2794).

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