Lewis Base Activation of Lewis Acids - Group 13. In Situ Generation and Reaction of Borenium Ions.

Lewis Base Activation of Lewis Acids - Group 13. In Situ Generation and Reaction of Borenium Ions.
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DOI:
10.1021/om400582k
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发表时间:
2013-11-25
期刊:
影响因子:
2.8
通讯作者:
Ueki Y
Ueki Y
中科院分区:
化学2区
文献类型:
--
作者:
Denmark SE;Ueki Y

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将多种刘易斯碱与9-BBN-NTf 2组合以确定生成硼鎓阳离子的要求。发现了五种不同类型的行为,但最有趣的是Et 3 N,DABCO,2,6-lutidine,或Ph 3 P =S的组合,即使在亚或超化学计量的量也只形成borenium离子。发现2,6-二甲基吡啶的9-BBN Borenium离子络合物在Et 3SiH存在下快速催化各种酮的硅氢加成反应。初步的机理实验表明,减少涉及Borenium离子活化的Et 3SiH,而不是酮。
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 behavior 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 was found to rapidly catalyze 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.
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