Synthesis of I(III)/S(VI) reagents and their reactivity in photochemical cycloaddition reactions with unsaturated bonds

Li Li; Kun Deng; Yajie Xing; Cheng Ma; Shao-Fei Ni; Zhaofeng Wang; Yong Huang

doi:10.1038/s41467-022-34401-7

Synthesis of I^(III)/S^(VI) reagents and their reactivity in photochemical cycloaddition reactions with unsaturated bonds

Nat Commun. 2022 Nov 3;13(1):6588. doi: 10.1038/s41467-022-34401-7.

Authors

Li Li¹, Kun Deng², Yajie Xing¹, Cheng Ma³, Shao-Fei Ni³, Zhaofeng Wang⁴, Yong Huang⁵

Affiliations

¹ Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, PR China.
² State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, PR China.
³ Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou, 515063, Guangdong, PR China.
⁴ State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, PR China. zfwangchem@hnu.edu.cn.
⁵ Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, PR China. yonghuang@ust.hk.

Abstract

The development of novel methodologies for the introduction of the sulfoxonium group under mild conditions is appealing but remains underexplored. Herein we report the synthesis of a class of hypervalent iodine reagents with a transferrable sulfoxonium group. These compounds enable mixed iodonium-sulfoxonium ylide reactivity. These well-defined reagents are examined in visible-light-promoted cyclization reactions with a wide range of unsaturated bonds including alkenes, alkynes, nitriles, and allenes. Two distinct cyclization pathways are identified, which are controlled by the substituent of the unsaturated bond. The cycloaddition protocol features simple operation, mild reaction conditions, and excellent functional group tolerance, affording a broad range of sulfoxonium-containing cyclic structures in moderate to excellent yields. Furthermore, the sufoxonium group in the product can be transformed into diverse functional groups and structural motifs via single electron transfer and transition-metal catalysis.

Abstract

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