Base-mediated homologative rearrangement of nitrogen-oxygen bonds of N-methyl-N-oxyamides.

ABSTRACT: Due to the well known reactivity of C(O)-N functionalities towards canonical C1-homologating agents (e.g. carbenoids, diazomethane, ylides), resulting in the extrusion of the N-centered fragment en route to carbonyl compounds, formal C1-insertions within N-O bonds still remain obscure. Herein, we document the homologative transformation of N-methyl-N-oxyamides - with high tolerance for diverse O-substituents - into N-acyl-N,O-acetals. Under controlled basic conditions, the N-methyl group of the same starting materials acts as a competent precursor of the methylene synthon required for the homologation. The logic is levered on the formation of an electrophilic iminium ion (via N-O heterolysis) susceptible to nucleo

SUBMITTER: Malik M 

PROVIDER: S-EPMC10530184 | biostudies-literature | 2023 Sep

REPOSITORIES: biostudies-literature