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

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

Minoru Uemura  1 , Iain D G Watson, Mikimoto Katsukawa, F Dean Toste
Affiliations

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

Minoru Uemura et al. J Am Chem Soc. .

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.

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Figures

Scheme 1
Scheme 1
Proposed Mechanisms
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References

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