Metathesis of P=C Bonds Catalyzed by N-Heterocyclic Carbenes

被引：6
|
作者：
Han, Zeyu [1 ]
Gates, Derek P. [1 ]
机构：
[1] Univ British Columbia, Dept Chem, 2036 Main Mall, Vancouver, BC V6T 1Z1, Canada
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2021年 / 27卷 / 59期
基金：
加拿大自然科学与工程研究理事会;
关键词：
carbenes; homogenous catalysis; main group elements; metathesis; phosphaalkenes; TERMINAL BORYLENE COMPLEXES; PHOSPHA-ORGANIC CHEMISTRY; PHOSPHINIDENE COMPLEXES; MOLECULAR-STRUCTURE; OLEFIN-METATHESIS; MULTIPLE BONDS; CHEMICAL-SHIFTS; REACTIVITY; WITTIG; MECHANISM;
D O I：
10.1002/chem.202102384
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The catalytic metathesis of C=C bonds is a textbook reaction that has no parallel in the widely studied area of multiple bonds involving heavier p-block elements. A high-yielding P=C bond metathesis of phosphaalkenes (ArP=CPh2, Ar=Mes, o-Tol, Ph) has been discovered that is catalyzed by N-heterocyclic carbenes (NHC=Me2IMe, (Me2IPr)-Pr-i). The products are cyclic oligomers formally derived from ArP=PAr [i. e. cyclo-(ArP)(n); n=3, 4, 5, 6] and Ph2C=CPh2. Preliminary mechanistic studies of this remarkable transformation have established NHC=PAr (Ar=Mes, o-Tol, Ph) as key phosphinidene transfer agents. In addition, novel cyclic intermediates, such as, cyclo-(ArP)(2)CPh2 and cyclo-(ArP)(4)CPh2 have also been observed. This work represents a rare application of non-metal-based catalysts for transformations involving main-group elements.
引用
收藏
页码：14594 / 14599
页数：6
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