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Synfacts 2014; 10(1): 0052
DOI: 10.1055/s-0033-1340440
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Enantioselective Rhodium-Catalyzed DYKAT of Racemic Allenes

Contributor(s):
Mark Lautens
,
Zafar Qureshi
Tran DN, Cramer N * École Polytechnique Fédérale de Lausanne, Switzerland
Rhodium-Catalyzed Dynamic Kinetic Asymmetric Transformations of Racemic Allenes by the [3+2] Annulation of Aryl Ketimines.

Angew. Chem. Int. Ed. 2013;
52: 10630-10634
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Further Information

Publication History

Publication Date:
13 December 2013 (online)

 
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Key words

rhodium - dynamic kinetic asymmetric transformation - allenes

Significance

Chiral amines are present in numerous biologically active compounds (see Book below). Starting from readily accessible racemic allenes, the authors were able to access indane structures containing chiral amines via a dynamic kinetic asymmetric transformation (DYKAT) in a [3+2] cycloaddition.


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Book

Chiral Amine Synthesis: T. C. Nugent, Ed.; Wiley-VCH: Weinheim, 2010.


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Comment

The rhodium hydride, formed by the initial directed C–H activation, adds across the ­racemic allene forming a rhodium allyl species. The rhodium allyl species can then interconvert via σ–π–σ isomerization leading to a chiral intermediate which adds to the imine (see below for a Review on axis-to-center chirality transfer).


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Review

N. Krause, C. Winter Chem. Rev. 2011, 111, 1994–2009.


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