Accessing chiral sulfones bearing quaternary carbon stereocenters via photoinduced radical sulfur dioxide insertion and Truce–Smiles rearrangement

• Published in: Nature communications Vol. 13; no. 1; pp. 7081 - 9
• Main Authors: Huang, Jiapian, Liu, Fei, Zeng, Ling-Hui, Li, Shaoyu, Chen, Zhiyuan, Wu, Jie
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 18.11.2022; Nature Publishing Group; Nature Portfolio
• Subjects: 639/638/403/935; 639/638/439/890; Accessibility; Asymmetry; Biocompatibility; Carbon; Catalysis; Chemistry; Functional groups; Humanities and Social Sciences; Insertion; Molecular Structure; multidisciplinary; Photoredox catalysis; Potassium; Science; Science (multidisciplinary); Stereoisomerism; Stereospecificity; Substrates; Sulfones; Sulfur; Sulfur Dioxide
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-022-34836-y

From the viewpoint of synthetic accessibility and functional group compatibility, photoredox-catalyzed sulfur dioxide insertion strategy enables in situ generation of functionalized sulfonyl radicals from easily accessible starting materials under mild conditions, thereby conferring broader application potential. Here we present two complementary photoinduced sulfur dioxide insertion systems to trigger radical asymmetric Truce–Smiles rearrangements for preparing a variety of chiral sulfones that bear a quaternary carbon stereocenter. This protocol features broad substrate scope and excellent stereospecificity. Aside from scalability, the introduction of a quaternary carbon stereocenter at position β to bioactive molecule-derived sulfones further demonstrates the practicality and potential of this methodology. The preparation of chiral sulfones featuring quaternary carbon stereocenters remains challenging. Here the authors report the synthesis of such compounds via a multicomponent reaction involving a photoinduced radical sulfur dioxide insertion followed by an asymmetric Truce–Smiles rearrangement.