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An efficient catalytic system was developed for the acetalization and ketalization of carbonyl compounds with polyhydric alcohols under mild solvent-free conditions. In the presence of 0.1 mol% CoCl2 and 0.2 mol% dimethylglyoxime at 70 °C under 5 KPa pressure for 1 h, 95.3% conversion of cyclohexanone and 100% selectivity of the corresponding cyclic ketal could be obtained, where TOF reached as high as 953 h−1. It is proposed that the in situ generated planartetracoordinate cobaloxime played the key role in the catalytic cycle and was responsible for the excellent catalytic performance.

Highly Efficient Acetalization and Ketalization Catalyzed by Cobaloxime under Solvent-Free Condition