C(sp³)-H oxygenation via alkoxypalladium(ii) species: an update for the mechanism.

ABSTRACT: Pd-catalyzed C(sp³)-H oxygenation has emerged as an attractive strategy for organic synthesis. The most commonly proposed mechanism involves C(sp³)-H activation followed by oxidative addition of an oxygen electrophile to give an alkylpalladium(iv) species and further C(sp³)-O reductive elimination. In the present study of γ-C(sp³)-H acyloxylation of amine derivatives, we show a different mechanism when tert-butyl hydroperoxide (TBHP) is used as an oxidant-namely, a bimetallic oxidative addition-oxo-insertion process. This catalytic model results in an alkoxypalladium(ii) intermediate from which acyloxylation and alkoxylation products are formed. Experimental and computational studies, including isolation of the putative post-oxo-insertion

SUBMITTER: Zhang S 

PROVIDER: S-EPMC8809414 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature