Lewis Base Activation of Lewis Acids: Group 13. In Situ Generation and Reaction of Boreniunn Ions

被引:37
|
作者
Denmark, Scott E. [1 ]
Ueki, Yusuke [1 ]
机构
[1] Univ Illinois, Dept Chem, Roger Adams Lab, Urbana, IL 61801 USA
基金
美国国家卫生研究院; 日本学术振兴会;
关键词
CATALYSIS; MECHANISM; HYDROSILYLATION; HYDROSILATION; THIIRANIUM; CHEMISTRY; BORINIUM;
D O I
10.1021/om400582k
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A variety of Lewis bases were combined with 9-BBN-NTf2 to establish the requirements for the generation of borenium cations. Five different types of behaviors were found, but the most interesting was the combination of Et3N, DABCO, 2,6-lutidine, or Ph3P=S, which formed borenium ions exclusively even in sub- or superstoichiometric quantities. The 9-BBN borenium ion complex of 2,6-lutidine rapidly catalyzes the hydrosilylation of a variety of ketones in the presence of Et3SiH. Preliminary mechanistic experiments suggest that the reduction involves borenium ion activation of Et3SiH and not the ketone.
引用
收藏
页码:6631 / 6634
页数:4
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