A formal synthesis of salinosporamide A is described. The tertiary
alcohol function in salinosporamide A was stereoselectively generated
via the substrate control by the reaction of a cyclic ketone derived
from d-glucose with Me3Al, and
subsequent Overman rearrangement of an allylic trichloroacetimidate
effectively constructed the tetrasubstituted carbon with nitrogen.
Formation of γ-lactam, followed by the introduction of
a cyclohexenyl unit furnished the Corey’s intermediate
of salinosporamide A.
stereoselective synthesis - carbohydrates - chiral
pool - rearrangements - pericyclic reactions