Four-Step One-Pot Catalytic Asymmetric Synthesis of Polysubstituted Tricyclic Compounds: Lipase-Catalyzed Dynamic Kinetic Resolution Followed by an Intramolecular Diels-Alder Reaction

Starting from readily available tertiary alcohols, four different reactions (a 1,3-migration of a hydroxy group, kinetic resolution, racemization, and an intramolecular Diels-Alder reaction) took place under co-catalysis by lipase and oxovanadium compounds in a one-pot process to produce polysubstituted tricyclic carbon frameworks in high yields and with high enantioselectivities. The key to the success of this process was the discovery that a silyl group attached to the terminal carbon of the vinyl moiety completely controls the direction of hydroxy group migration

Automated summary

This study successfully carried out four different reactions (1,3-migration of a hydroxy group, kinetic resolution, racemization, and an intramolecular Diels-Alder reaction) from readily available tertiary alcohols in a one-pot process with high yields and high enantioselectivities, under the co-catalysis of lipase and oxovanadium compounds. The key discovery was that a silyl group attached to the vinyl moiety's terminal carbon controlled the direction of hydroxy group migration.