MnO2 -Promoted Oxidative Radical Sulfonylation of Haloalkynes with Sulfonyl Hydrazides: C(sp)-S Bond Formation towards Alkynyl Sulfones.

A catalyst-free oxidative radical sulfonylation of haloalkynes with sulfonyl hydrazides is reported. It represents an example of C(sp)-S bond formation using sulfonyl hydrazides as sulfonyl radical sources. Various alkynyl sulfones were synthesized in moderate to good yields. Having MnO2 as the oxidant is very critical for this transformation. Remarkably, the self-coupling reaction of haloalkynes through C(sp)-C(sp) bond formation is significantly inhibited under the standard reaction conditions.