Gold(I)-catalyzed enantioselective synthesis of benzopyrans via rearrangement of allylic oxonium intermediates

Minoru Uemura; Iain D G Watson; Mikimoto Katsukawa; F Dean Toste

doi:10.1021/ja900155x

Gold(I)-catalyzed enantioselective synthesis of benzopyrans via rearrangement of allylic oxonium intermediates

J Am Chem Soc. 2009 Mar 18;131(10):3464-5. doi: 10.1021/ja900155x.

Authors

Minoru Uemura¹, Iain D G Watson, Mikimoto Katsukawa, F Dean Toste

Affiliation

¹ Department of Chemistry, University of California, Berkeley, California 94720, USA.

Abstract

The first transition metal catalyzed asymmetric carboalkoxylation reaction of propargyl esters is described. The (R)-MeO-DTBM-BIPHEP(AuCl)(2)-catalyzed reactions allow for the construction of benzopyrans containing quaternary stereocenters with excellent enantioselectivity. Experimental evidence supports a mechanism proceeding via the generation of a stabilized carbocation from an allylic oxonium intermediate and subsequent trapping by a chiral allylgold(I) spieces.

Publication types

Research Support, N.I.H., Extramural
Research Support, Non-U.S. Gov't

MeSH terms

Benzopyrans / chemistry*
Catalysis
Gold / chemistry*
Stereoisomerism

Substances

Benzopyrans
Gold

Abstract

Publication types

MeSH terms

Substances

Grants and funding