Dynamic Kinetic Spiroketalization/Oxa-Michael Addition Cascade of Alkoxyboronates and Peroxyacetals: Enantio- and Diastereoselective Synthesis of Benzannulated Spiroketals.

ABSTRACT

A unified dynamic kinetic spiroketalization/enantioselective oxa-Michael addition cascade of an aromatic ketone tethered to an alkoxyboronate and an enone moiety has been developed using cinchona alkaloid based amino-thiourea/squaramide organocatalysts to provide isobenzofuran-based benzannulated spiroketals with high diastereoselectivities and excellent enantioselectivities. Further, a dynamic kinetic peroxy-hemiacetalization/dynamic kinetic spiroketalization/enantioselective oxa-Michael addition cascade of the above substrates provides the corresponding exo-peroxy-benzannulated spiroketals with outstanding enantio- and diastereoselectivities.