Post-functionalization of dibenzothiophene to functionalized biphenyls via a photoinduced thia-Baeyer-Villiger oxidation.

Abstract

The Baeyer-Villiger reaction is used extensively in organic chemistry. Sila- and bora-variants have also been documented widely, with these processes underpinning, for example, the Fleming-Tamao oxidation and hydroborative alkene hydration, respectively. By contrast, the development of thia-Baeyer-Villiger reactions involving sulfoxides has long been considered unlikely because competitive oxidation to the sulfone occurs exclusively. Here, we disclose a photoinduced thia-Baeyer-Villiger-type oxidations; specifically, we find that exposure of dibenzothiophene (DBT) derivatives to an iron porphyrin catalyst under Ultraviolet irradiation in the presence of t-BuOOH generates sulfinic esters in up to 87% yield. The produced sulfinic esters are transformed to a variety of biphenyl substrates including biphenyl sulfoxides, sulfones and sulfonamides in 1-2 steps. These results provide a mild process for the selective functionalization of sulfur compounds, and offer a biomimetic approach to convert DBT into 2-hydroxybiphenyl under controllable stepwise pathway. Based upon experimental evidences and DFT calculation, a mechanism is proposed.