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

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.