Photoredox‐Catalyzed Preparation of Sulfones Using Bis‐Piperidine Sulfur Dioxide – An Underutilized Reagent for SO2 Transfer

• Published in: Chemistry : a European journal Vol. 30; no. 12; pp. e202303976 - n/a
• Main Authors: Griffiths, Oliver M., Esteves, Henrique A., Emmet, Darcy C., Ley, Steven V.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 26-02-2024
• Subjects: Aromatic compounds; Bromides; Catalysis; Photoredox catalysis; Piperidine; Reagents; SO2 surrogate; sulfinates; Sulfonamides; Sulfones; Sulfur; Sulfur dioxide; Sulfur dioxide recovery
• DOI: 10.1002/chem.202303976
• EISSN: 1521-3765
• ISSN: 0947-6539

Sulfonyl groups are widely observed in biologically relevant molecules and consequently, SO2 capture is an increasingly attractive method to prepare these sulfonyl‐containing compounds given the range of SO2‐surrogates now available as alternatives to using the neat gas. This, along with the advent of photoredox catalysis, has enabled mild radical capture of SO2 to emerge as an effective route to sulfonyl compounds. Here we report a photoredox‐catalyzed cross‐electrophile sulfonylation of aryl and alkyl bromides making use of a previously under‐used amine‐SO2 surrogate; bis(piperidine) sulfur dioxide (PIPSO). A broad selection of alkyl and aryl bromides were photocatalytically converted to their corresponding sulfinates and then trapped with various electrophiles in a one‐pot multistep procedure to prepare sulfones and sulfonamides.
A photoredox‐catalyzed one‐pot sulfone preparation is reported from alkyl bromides activated by silane‐mediated halogen atom transfer. In the process, a previously unutilized SO2 adduct bis(piperidine) sulfur dioxide – or PIPSO – was found to be the best source of SO2 for radical capture under the reaction conditions. Alkyl and aryl sulfones were prepared as well as sulfonylated APIs.