Rare-Earth-Catalyzed Selective 1,4-Hydrosilylation of Branched 1,3-Enynes Giving Tetrasubstituted Silylallenes

被引：43

作者：

Chen, Wufeng ^{[1
,2
]}

Jiang, Chunhui ^{[1
,2
]}

Zhang, Jianying ^{[1
,2
]}

Xu, Jiaqi ^{[1
,2
]}

Xu, Lin ^{[1
,2
]}

Xu, Xiufang ^{[1
,2
]}

Li, Jianfeng ^{[1
,2
]}

Cui, Chunming ^{[1
,2
]}

机构：

[1] Nankai Univ, State Key Lab Elemento Organ Chem, Tianjin 300071, Peoples R China

[2] Nankai Univ, Coll Chem, Tianjin 300071, Peoples R China

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2021年 / 143卷 / 33期

基金：

中国国家自然科学基金;

关键词：

STEREOSELECTIVE HYDROSILYLATION; REGIOSELECTIVE HYDROSILYLATION; CYCLIZATION REACTIONS; ASYMMETRIC-SYNTHESIS; ALLENES; ALKYNES; POLYMERIZATION; ALKENES; HETEROAROMATICS; ACTIVATION;

D O I：

10.1021/jacs.1c04689

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Allenes are versatile synthons in organic synthesis and medicinal chemistry because of their diverse reactivities. Catalytic 1,4-hydrosilylation of 1,3-enynes may present the straightforward strategy for synthesis of silylallenes. However, the transition-metal-catalyzed reaction has not been successful due to poor selectivity and very limited substrate scopes. We report here the efficient and selective 1,4-hydrosilylation of branched 1,3-enynes enabled by the ene-diamido rare-earth ate catalysts using both alkyl and aryl hydrosilanes, leading to the exclusive formation of tetrasubstituted silylallenes. Deuteration reaction, kinetic study, and DFT calculations were conducted to investigate the possible mechanism, revealing crucial roles of high Lewis acidity, large ionic radius, and ate structure of the rare-earth catalysts.

引用

页码：12913 / 12918

页数：6

共 71 条

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