Synthesis of Racemic and Enantiomerically Enriched α-Oxyfunctionalized Benzocyclanones and Chromanones by Dimethyldioxirane and Dimethyldioxirane/Mn(III) salen System

Summary.

Enolacetates of benzocyclanones and chromanones were synthesized and treated with dimethyldioxirane and the asymmetric oxidizing system dimethyldioxirane/chiral, non-racemic Mn(III) salen complex/axial ligand. The latter reagent resulted in the corresponding enantiomerically enriched cyclic α-hydroxy ketones and their acetates in moderate-to-good yields and modest enantioselectivity under mild and neutral conditions from tetralone and chromanone. On the contrary, flavanone provided poor yields due to the competitive C–H insertion at position 2. The use of R,R-Mn(III)salen catalyst induced an S absolute configuration at the position α in the whole series.