Photocatalytic Aerobic Oxidative Ring Expansion of Cyclic Ketones to Macrolactones by Cerium and Cyanoanthracene Catalysis

Abstract We describe a cerium‐catalyzed aerobic oxidative ring expansion for the expedient construction of synthetically challenging macrolactones under visible‐light conditions. Cyanoanthracene has been employed as co‐catalyst to accelerate the turnover of the cerium cycle leading to a fast conversion within 20 min of irradiation. Taking advantage of the high efficiency and operationally simple conditions, a collection of over 100 macrolactones equipped with ring systems ranging from 9‐ to 19‐membered macrocycles have been prepared from simple building blocks. Moreover, the enabling potential of this strategy to simplify the generation of molecular complexity has been demonstrated through the concise synthesis of sonnerlactone.