Mechanistic Basis for Efficient, Site-Selective, Aerobic Catalytic Turnover in Pd-Catalyzed C-H Imidoylation of Heterocycle-Containing Molecules.

ABSTRACT: A recently reported Pd-catalyzed method for oxidative imidoylation of C-H bonds exhibits unique features that have important implications for Pd-catalyzed aerobic oxidation catalysis: (1) The reaction tolerates heterocycles that commonly poison Pd catalysts. (2) The site selectivity of C-H activation is controlled by an N-methoxyamide group rather than a suitably positioned heterocycle. (3) A Pd⁰ source, Pd₂(dba)₃ (dba = dibenzylideneacetone), is superior to Pd(OAc)₂ as a precatalyst, and other Pd^II sources are ineffective. (4) The reaction performs better with air, rather than pure O₂. The present study elucidates the origin of these features. Kinetic, mechanistic, and in situ spectroscopic studies establish that Pd^II<

SUBMITTER: Tereniak SJ 

PROVIDER: S-EPMC5902801 | biostudies-literature | 2017 Oct

REPOSITORIES: biostudies-literature