Molecular Iodine‐Mediated Functionalization of α‐Carbonyl Sulfoxonium Ylides with Thiocyanates, Xanthates, and Dithiocarbamates

A method for synthesizing α-xanthates, α-thiocyanates, and α-dithiocarbamates has been developed. By employing molecular iodine and the potassium salts of xanthates, thiocyanate, and dithiocarbamates, a wide range of products is obtained, with yields reaching up to 83%. Sulfoxonium ylides derived from esters, ketones, amides, heterocycles, and steroids are successfully functionalized under these conditions.

In this work, a straightforward, rapid, and cost-effective protocol is presented for synthesizing three distinct classes of α-functionalized sulfoxonium ylides—α-xanthate, α-thiocyanate, and α-dithiocarbamate—via molecular iodine-mediated reactions. This method demonstrates broad substrate tolerance, including heterocycles and steroids, delivering 25 examples with yields of up to 83%. Experimental studies revealed that iodine reacts with xanthates to form disulfides, which subsequently act as electrophiles for nucleophilic attack by the ylide.

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