Mechanism of catalytic functionalization of primary C-H bonds using a silylation strategy

Abhishek Parija; Raghavan B Sunoj

doi:10.1021/ol401597t

Mechanism of catalytic functionalization of primary C-H bonds using a silylation strategy

Org Lett. 2013 Aug 16;15(16):4066-9. doi: 10.1021/ol401597t. Epub 2013 Aug 7.

Authors

Abhishek Parija¹, Raghavan B Sunoj

Affiliation

¹ Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.

PMID: 23924401
DOI: 10.1021/ol401597t

Abstract

The mechanism of Ir-catalyzed γ-functionalization of a primary sp(3)(C-H) bond in 2-methyl cyclohexanol is examined using the density functional theory (M06). The nature of the active catalyst for the initial silylation of alcohol is identified as the monomer derived from [Ir(cod)OMe]2 while that for γ-sp(3)(C-H) activation leading to oxasilolane is [IrH(nbe)(phen)]. The rate-determining step is found to involve Si-C coupling through reductive elimination.