Asymmetric Organocatalyzed Reaction Sequence To Synthesize Chiral Bridged and Spiro-Bridged Benzofused Aminals via Divergent Pathways.

A highly efficient asymmetric organocatalysis-triggered reaction sequence is developed. 2-Hydroxy cinnamaldehydes and cyclic N-sulfonyl ketimines were both used as multisite substrates (more than two reactive sites) to access structurally diverse chiral bridged and spiro-bridged benzofused aminal derivatives, where an inseparable equilibrating mixture of isomers can be regioselectively converted into bridged benzofused aminals with different ring connectivities via divergent pathways. Several stereoselective transformations of the resulted bridged aminals are presented.