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Synfacts 2011(5): 0555-0555  
DOI: 10.1055/s-0030-1259850
Organo- and Biocatalysis
© Georg Thieme Verlag Stuttgart ˙ New York

Dithiophosphoric Acid Catalyzed Hydro-amination of Dienes

Contributor(s): Benjamin List, Steffen Müller
N. D. Shapiro, V. Rauniyar, G. L. Hamilton, J. Wu, F. D. Toste*
University of California, Berkeley, USA
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Publication History

Publication Date:
15 April 2011 (online)

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Significance

Toste and co-workers report the highly enantioselective hydroamination of 1,2- and 1,3-dienes catalyzed by dithiophosphoric acids 1. The reaction is proposed to be initiated by protonation of the diene and subsequent addition of the catalyst in syn fashion. This adduct is cleaved again through an intramolecular SN2′ reaction, in which the internal nitrogen nucleophile replaces the dithiophosphate. This activation mode, involving covalent binding of the catalyst to the substrate, is supported by mechanistic studies. Furthermore, the authors extended successfully their catalytic system to hydroarylation reactions.

Review: M. Terada Synthesis 2010, 1929-1982.