Asymmetric photocycloaddition of naphthamide with a diene using the provisional molecular chirality in a chiral crystal.

N-(2-Methoxy-1-naphthoyl)piperidine afforded chiral crystals by spontaneous crystallization, and the molecular chirality of the crystals was retained after dissolving them in a cooled solvent. An asymmetric photocycloaddition reaction with a diene was performed using the provisional chiral molecular conformation derived from these chiral crystals.

An asymmetric S(N)Ar reaction using the molecular chirality in a crystal.

An asymmetric S(N)Ar reaction was performed by using molecular chirality generated and amplified by the spontaneous crystallization of achiral naphthamides; the chirality was retained in a cold solution, caused by slow racemization, and was transferred to stable axially chiral materials with high enantiomeric excesses.

Diastereoselective photocycloaddition using memory effect of molecular chirality controlled by crystallization.

Naphthamides derived from L-proline, which exist as a mixture of several diastereomers in solution, converged to single diastereomer by crystallization, and the conformational transformation was controlled after the crystals were dissolved in the solvent at low temperature, where the frozen conformation was retained long enough for subsequent asymmetric reaction.

Absolute asymmetric synthesis by nucleophilic carbonyl addition using chiral crystals of achiral amides.

Reaction of the chiral crystals of the achiral amides with n-butyllithium in toluene at -80 degrees C gave optically active alcohols in 17-84% ee.