Axially Chiral, Electrophilic Fluorophosphonium Cations: Synthesis, Lewis Acidity, and Reactivity in the Hydrosilylation of Ketones

被引：17

作者：

Suesse, Lars ^{[1
]}

LaFortune, James H. W. ^{[2
]}

Stephan, Douglas W. ^{[1
,2
]}

Oestreich, Martin ^{[1
]}

机构：

[1] Tech Univ Berlin, Inst Chem, Str 17 Juni 115, D-10623 Berlin, Germany

[2] Univ Toronto, Dept Chem, 80 St George St, Toronto, ON M5S 3H6, Canada

来源：

ORGANOMETALLICS | 2019年 / 38卷 / 03期

基金：

加拿大自然科学与工程研究理事会;

关键词：

B(C6F5)(3)-CATALYZED HYDROSILYLATION; TRANSFER HYDROGENATION; BASIS-SETS; BORON; HYDROSILATION; REDUCTIONS; MECHANISM; CATALYSIS; ALDEHYDES; LIGANDS;

D O I：

10.1021/acs.organomet.8b00912

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Axially chiral [(C6F5)(3)PF][B(C6F5)(4)] analogues based on dihydrophosphepines with a binaphthyl backbone were prepared and structurally characterized by X-ray diffraction analysis. Computational calculations of FIA and GEI values attest that these new fluorophosphonium cations have a higher Lewis acidity compared to the ubiquitous B(C6F5)(3). Furthermore, application of these highly electrophilic compounds in the catalytic hydrosilylation of ketones and an investigation of the mechanism lead to a refined picture of the role of highly electrophilic fluorophosphonium cations.

引用

页码：712 / 721

页数：10