Herein, a donor/acceptor‐free carbene insertion reaction of an S–S bond through a radical process is presented. This catalyst‐free reaction was thermally induced and provided the dithioketal products in moderate to high yields. A mechanism involving radical intermediates was proposed according to the computational study, and these intermediates were verified experimentally and intercepted for the first time by using a cross‐coupling reaction.
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Zheng et al. (2016) studied this question.
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