Mechanistic Origin of Chemo- and Regioselectivity of Nickel-Catalyzed [3+2+2] Cyclization Reaction

被引：40

作者：

Komagawa, Shinsuke ^{[1
,2
,3
]}

Wang, Chao ^{[1
,2
,3
]}

Morokuma, Keiji ^{[4
,5
,6
]}

Saito, Shinichi ^{[7
]}

Uchiyama, Masanobu ^{[1
,2
,3
]}

机构：

[1] Univ Tokyo, Grad Sch Pharmaceut Sci, Bunkyo Ku, Tokyo 1130033, Japan

[2] RIKEN, RIKEN Ctr Sustainable Resource Sci, Adv Elements Chem Res Team, Wako, Saitama 3510198, Japan

[3] RIKEN, Elements Chem Lab, Wako, Saitama 3510198, Japan

[4] Emory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA

[5] Emory Univ, Dept Chem, Atlanta, GA 30322 USA

[6] Kyoto Univ, Fukui Inst Fundamental Chem, Nishihiraki, Kyoto 6068103, Japan

[7] Tokyo Univ Sci, Fac Sci, Dept Chem, Shinjuku Ku, Tokyo 1628601, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 39期

关键词：

ETHYL CYCLOPROPYLIDENEACETATE; CYCLOADDITION REACTIONS; DENSITY FUNCTIONALS; ORGANIC-SYNTHESIS; 7-MEMBERED RINGS; CARBON-DIOXIDE; ALKYNES; COMPLEXES; CYCLOTRIMERIZATION; COCYCLIZATION;

D O I：

10.1021/ja4068468

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A density functional theory (DFT) study was performed to elucidate the mechanism of the Ni-catalyzed [3 + 2 + 2] Cyclization reaction of cyclo-propylideneacetate with two alkynes. A systematic search showed that the nature of the alkynes determines the choice between two reaction pathways and hence the regioselectivity. Strongly electron-deficient acetylenes preferentially afford 2,5-disubstituted products via nickel-acyclopentadienes generated by [2 + 2] cocyclization, whereas normal alkynes afford 3,4 or 3,5-products via an unprecedented pathway involving a [3 + 2] nickelacycle intermediate.

引用

页码：14508 / 14511

页数：4

共 52 条

[1] Cobalt-catalyzed cyclotrimerization of alkynes: The answer to the puzzle of parallel reaction pathways [J].