Department of Chemistry, Center for Catalysis, University of Florida , Gainesville, Florida 32611, United States.
Chem Rev. 2016 Jul 27;116(14):8105-45. doi: 10.1021/acs.chemrev.6b00054. Epub 2016 Jul 1.
This review describes organometallic compounds and materials that are capable of mediating a rarely encountered but fundamentally important reaction: β-alkyl elimination at the metal-Cα-Cβ-R moiety, in which an alkyl group attached to the Cβ atom is transferred to the metal or to a coordinated substrate. The objectives of this review are to provide a cohesive fundamental understanding of β-alkyl-elimination reactions and to highlight its applications in olefin polymerization, alkane hydrogenolysis, depolymerization of branched polymers, ring-opening polymerization of cycloalkanes, and other useful organic reactions. To provide a coherent understanding of the β-alkyl elimination reaction, special attention is given to conditions and strategies used to facilitate β-alkyl-elimination/transfer events in metal-catalyzed olefin polymerization, which provide the well-studied examples.
β-烷基消除反应,其中连接在 Cβ 原子上的烷基基团转移到金属或配位的底物上。这篇综述的目的是提供对β-烷基消除反应的连贯的基本理解,并强调其在烯烃聚合、烷烃氢解、支化聚合物的解聚、环烷烃的开环聚合和其他有用的有机反应中的应用。为了对β-烷基消除反应有一个连贯的理解,特别关注了在金属催化的烯烃聚合中促进β-烷基消除/转移反应的条件和策略,这些反应提供了经过充分研究的例子。