A self-hydrosilylation of phosphanylhydrosilylalkynes promoted by B(C6F5)3? An experimental and mechanistic study

被引：7

作者：

Huang, Yanting ^{[1
]}

Wang, Xiaoping ^{[1
]}

Li, Yan ^{[2
]}

Yang, Ming-Chung ^{[3
]}

Su, Ming-Der ^{[3
,4
]}

Zhu, Hongping ^{[1
]}

机构：

[1] Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Natl Engn Lab Green Chem Prod Alcohols Ethers Est, Xiamen 361005, Peoples R China

[2] Hangzhou Normal Univ, Minist Educ, Key Lab Organosilicon Chem & Mat Technol, Hangzhou 311121, Zhejiang, Peoples R China

[3] Natl Chiayi Univ, Dept Appl Chem, Chiayi 60004, Taiwan

[4] Kaohsiung Med Univ, Dept Med & Appl Chem, Kaohsiung 80708, Taiwan

来源：

CHEMICAL COMMUNICATIONS | 2019年 / 55卷 / 10期

基金：

中国国家自然科学基金;

关键词：

H-B BRIDGES; LEWIS; HYDROSILATION; 1,1-ORGANOBORATION; ACTIVATION; ELEMENTS; ALKYNES;

D O I：

10.1039/c8cc09022j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Phosphanylhydrosilylalkynes Me2HSiC?CPAr2 (Ar = Ph, 1a; 4-MeC6H4, 1b) were synthesized, which reacted with B(C6F5)(3) to produce alkenes [(E)-(C6F5)(3)BCH?C(PAr2)SiMe2](2) (2a and 2b) and (Z)-(C6F5)(2)BCH?C(PAr2)SiMe2(C6F5) (3a and 3b). The formation of 2a (or 2b) involved a Wrackmeyer's SiHMe2 migration followed by Si-H addition across the C?C bond, whereas, that of 3a (or 3b) involved a similar mechanism with a further C6F5 migration. The B(C6F5)(3)-promoted reaction of the Si-centered geminal H and C?C groups is thus realized, which may be considered as a self-hydrosilylation. Mechanistic studies by both variable temperature NMR spectroscopy and DFT calculations were accomplished.

引用

页码：1494 / 1497

页数：4

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