Unique Thia‐Baeyer–Villiger‐Type Oxidation of Dibenzothiophene Sulfoxides Derivatives

Abstract

The present research has demonstrated that selective C−S bond cleavages of dibenzothiophene and its derivatives are feasible by thia‐Baeyer–Villiger type oxidation, i. e. the oxygen insertion process within a sulfoxide‐carbon linkage, in the presence of porphyrin iron (III) and by ultraviolet irradiation originating from sunlight, high pressure Hg‐lamp or residentially germicidal ultraviolet lamp under very mild conditions. This reaction with tert‐butylhydroperoxide at 30.0 °C leads to dibenzo[1,2]oxathiin‐6‐oxide (PBS) in 83.2 % isolated yield or its hydrated products, 2‐(2‐hydroxyphenyl)‐benzenesulfinic derivatives (HPBS) in near 100 % yield based HPLC data. PBS and HPBS are a type of biological products detected on the C−S bond cleavage step through various oxidative biodesulfurization (OBDS) pathways, and are useful synthetic intermediates and fine chemicals. These observations may contribute on understanding delicately molecular aspect of OBDS in the photosynthesis system, expanding the C‐S cleavage chemistry of S‐heterocyclic compounds and approaching toward biomemic desulfurization with respect to converting sulfur contaminants to chemically beneficial blocks as needed and performing under the ambient conditions.

Two‐step Two‐intermediate Photorelease Bolm‐McCulla Reaction: Dual Release of Nitrene and Atomic Oxygen Reactive Intermediates

“…sulfilimines and sulfonium ylides). Researchers also know about the processes that compete with S-X photocleavage, including a-cleavage, hydrogen abstraction and stereo-mutation, where aromatic content at the transition state in S-X inversion can enhance photorelease (41)(42)(43)(44)(45)(46)(47)(48). The reaction for the tandem formation of reactive intermediates is often overlooked in photochemistry and physical organic chemistry, where the use of experimental and theoretical work is beneficial.…”

Conducting 1D nanostructures from light-stimulated copper-metalated porphyrin–dibenzothiophene

“…Alternatively, in this report the thianthrene group is replaced by dibenzothiophene as an electron donor due to the presence of thiophene which enables easy oxidation upon light irradiation. [36][37][38][39][40][41] Thus, we designed three p-conjugated porphyrin derivatives consisting of free base, copper-metalated and zinc-metalated porphyrin-dibenzothiophene systems (P Fb -DBT, P Zn -DBT and P Cu -DBT) (Fig. 1a).…”