受阻路易斯酸碱对催化的富烯的硅氢化反应及硅烷介导的富烯氢化反应。
Frustrated Lewis pair catalyzed hydrosilylation and hydrosilane mediated hydrogenation of fulvenes.
作者信息
Tamke Sergej, Daniliuc Constantin-G, Paradies Jan
机构信息
Karlsruhe Institute of Technology, Institute of Organic Chemistry, Fritz-Haber-Weg 6, 76131, Karlsruhe, Germany.
出版信息
Org Biomol Chem. 2014 Dec 7;12(45):9139-44. doi: 10.1039/c4ob01346h.
The frustrated Lewis pair (FLP) mediated hydrosilylation of pentafulvenes is described yielding allyl silanes with high regioselectivity in excellent yields. While phenyl substituted allyl silanes undergo B(C6F5)3-mediated rearrangement to vinyl silanes, dimethyl derivatives experience FLP-catalyzed hydrogenation followed by an unprecedented protodesilylation. This observation allowed the metal-free hydrogenation of 6,6-dimethylfulvene to iso-propyl cyclopentene according to a FLP-catalyzed triple domino reaction consisting of hydrosilylation, hydrogenation and protodesilylation. The mechanisms were investigated by deuteration experiments.
描述了受阻路易斯酸碱对（FLP）介导的戊搭烯的硅氢化反应，该反应以优异的区域选择性和高产率生成烯丙基硅烷。虽然苯基取代的烯丙基硅烷会发生B(C6F5)3介导的重排生成乙烯基硅烷，但二甲基衍生物会经历FLP催化的氢化反应，随后是前所未有的原硅烷基化反应。这一发现使得6,6-二甲基戊搭烯能够通过由硅氢化、氢化和原硅烷基化组成的FLP催化的三重多米诺反应实现无金属氢化生成异丙基环戊烯。通过氘代实验对反应机理进行了研究。
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