Synthesis of Deoxyaminosugar Cyclohexyl-L-callipeltose and Its Diastereomer Using Pd-Catalyzed Asymmetric Hydroalkoxylation

Abstract

Cyclohexyl-L-callipeltose, an aminodeoxysugar subunit of Callipeltoside A, was synthesized in six steps and 40% overall yield from readily available (S)-4-methylpent-4-en-2-ol and cyclohexyloxyallene. The signature step is represented by Pd-catalyzed asymmetric intermolecular hydroalkoxylation that generates the key dihydropyran intermediate upon combination with the ring-closing metathesis reaction. Notably, an unnatural diastereomer of the target compound could also be obtained with comparable efficiency simply by using the enantiomeric ligand.