Steric bulkness of diamondoidyl substituents

Abstract

The influence of the diamondoidyl substituent on the reaction center was investigated experimentally and computationally. Calculations were provided at DFT and DFT-D,using B3LYP, B97D and M062X functionals. Experimental investigation was made by studying the Corey-Chaykovsky reaction. The latter was explored with dimethylsulfoxonium methylide and diamondoidyl ketones, which has different distance between the carbonyl group and the cage. Diamondoidyl substituent was shown to have negligible effect on the reactive center within 2 CH2 groups. While in ketones, bearing one CH2 group between cage and carbonyl, it hampers tetrahedization of the reactive center. In case of methyl diamondoidyl ketones the cage hinders the access of the reagent.