Catalytic Dicyanative [4+2] Cycloaddition Triggered by Cyanopalladation of Conjugated Enynes under Aerobic Conditions

被引：35

作者：

Arai, Shigeru ^{[1
]}

Koike, Yuka ^{[1
]}

Hada, Hirohiko ^{[1
]}

Nishida, Atsushi ^{[1
]}

机构：

[1] Chiba Univ, Grad Sch Pharmaceut Sci, Inage Ku, Chiba 2638522, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 13期

关键词：

CARBON TRIPLE BONDS; INTRAMOLECULAR CYANOBORATION; STEREOSELECTIVE SYNTHESIS; TRIMETHYLSILYL CYANIDE; TERMINAL ACETYLENES; C-C; ALKYNES; ARYLCYANATION; ARYLACETYLENES; ACTIVATION;

D O I：

10.1021/ja910451j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A palladium-catalyzed dicyanative [4+2] cycloaddition reaction using dienynes with TMSCN under aerobic conditions is described. This new reaction triggered by the cyanopalladation of terminal alkynes includes regioselective direct cyanation to C-C triple bonds by TMSCN to give pi-allyl Pd intermediates, which promotes 5-exo followed by 6-endo cyclization. This protocol enables (1) the formation of four C-C bonds through one operation, (2) the construction of highly functionalized cyclohexene rings, and (3) the generation of five contiguous stereogenic centers in one operation. The intermolecular cycloaddition reaction between a conjugated enyne and methyl acrylate also proceeded in a regioselective fashion to give multifunctionalized carbocycles.

引用

页码：4522 / +

页数：3

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