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.
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页码：712 / 721
页数：10
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