Green Chemistry Approach toward the Regioselective Synthesis of α,α-Disubstituted Allylic Amines.

Molybdenum-catalyzed allylic substitution reactions are known to provide direct and practical ways to construct new carbon-carbon bonds and privileged compounds. However, due to the lack of reports on carbon-heteroatom bond formation as a common deficiency, these reactions still face a great challenge. Described herein is a robust and convenient molybdenum-catalyzed regioselective allylic amination of tertiary allylic carbonates with an amine as the heteroatom nucleophile. Both aromatic and aliphatic amines react with various tertiary allylic alcohol derivatives to deliver the desired α,α-disubstituted allylic amines in high yield with complete regioselectivity. In addition, ethanol as the green solvent, a recyclable catalyst system through simple centrifugation techniques, and simple handling procedures make the current approach green, economic, and sustainable.