Gold(I)-Catalyzed Enantioselective Synthesis of Benzopyrans via Rearrangement of Allylic Oxonium Intermediates

被引：139

作者：

Uemura, Minoru ^{[1
]}

Watson, Iain D. G. ^{[1
]}

Katsukawa, Mikimoto ^{[1
]}

Toste, F. Dean ^{[1
]}

机构：

[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 10期

关键词：

CATALYZED CYCLOISOMERIZATION REACTIONS; GOLD CATALYSIS; INTRAMOLECULAR CARBOALKOXYLATION; SIGMATROPIC REARRANGEMENT; PROPARGYLIC CARBOXYLATES; ALKYNES; YLIDES; PLATINUM; CYCLOPROPANATION; ANNULATION;

D O I：

10.1021/ja900155x

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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.

引用

页码：3464 / +

页数：3

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