Stereodivergent Deacylative Mizoroki–Heck Reaction of Unstrained Ketones

Abstract Alkene structures represent one of the most functional and widely used in organic synthesis, drug design, and material science. However, developing a practical strategy to produce such high‐valued chemicals from widely abundant materials, such as ketones, remains elusive. Herein, we present a stereodivergent deacylative Mizoroki–Heck reaction of methyl ketones and cyclic ketones to furnish both E ‐ and Z ‐configured alkenes via dual photoredox/cobalt catalysis. Interestingly, the tunable E / Z ‐selectivity is achieved by energy transfer catalysis via the judicious choice of photocatalyst. This versatile strategy features a broad substrate scope with excellent functional group tolerance and is suitable for late‐stage modification of complex molecules and the one‐pot operation. It also expands the reaction profiles of both deacylative transformation and photoredox/cobalt catalysis.