Vicinal Dicarbonyl Reprogramming via Molybdenum-Catalyzed Formal C(O)-C(O) Bond Cleavage

Efficient C-C bond activation and transformation methods provide powerful strategies for constructing organic molecular frameworks. However, the development of general and efficient transition-metal-catalyzed C-C bond activation strategies remains a significant challenge. Herein, we report a molybdenum catalytic strategy for efficient and enantioselective formal C(O)-C(O) bond cleavage and recombination, thus reprogramming vicinal dicarbonyls to 1,4-dicarbonyls. Enabled by a powerful Mo-catalytic platform, the reactions proceeded with generally good yields, good regioselectivity, and excellent diastereoselectivity. Mechanistic studies suggested that a Mo-catalyzed stepwise radical [2 + 2] cycloaddition pathway was plausibly involved in the intramolecular formal C(O)-C(O) bond cleavage reaction. Furthermore, an array of chiral 1,4-dicarbonyl products was obtained with good enantioselectivity and excellent diastereoselectivity when a simple chiral salan-Mo catalyst was used as the chiral catalyst. This strategy not only offers an efficient catalytic platform for vicinal dicarbonyl reprogramming but also opens new avenues for the applications of chiral salan-Mo complexes in asymmetric catalysis.