Xanthate‐Based Pathways to Ketones

ABSTRACT This brief review describes applications of the radical chemistry of xanthates developed in the author's laboratory for the synthesis of open‐chain and cyclic ketones. Most direct and general are additions of α‐ketonyl xanthates to alkenes, but β‐ketonyl and S ‐acyl‐xanthates are also valuable reagents. Several novel allylation reactions can be used in conjunction with xanthates to provide a variety of ketones. The radical addition step can then be followed by various radical and non‐radical post‐modification steps to furnish more elaborate compounds. This chemistry is flexible, versatile, highly tolerant of numerous functional groups, and, importantly, allows intermolecular additions to be accomplished on non‐activated, electronically unbiased alkenes. These properties open synthetic pathways and retrosynthetic analyses hitherto unavailable.