Fundamentals of beta-alkyl elimination

New paper from former post-doc, Matt O'Reilly.

http://pubs.acs.org/doi/abs/10.1021/acs.chemrev.6b00054

β-Alkyl Elimination: Fundamental Principles and Some Applications

Matthew E. O’Reilly, Saikat Dutta, and Adam S. Veige^*

Department of Chemistry, Center for Catalysis, University of Florida, Gainesville, Florida 32611, United States

Chem. Rev., 2016, 116 (14), pp 8105–8145

DOI: 10.1021/acs.chemrev.6b00054

Publication Date (Web): July 1, 2016

Abstract

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–C_α–C_β–R moiety, in which an alkyl group attached to the C_β 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.