Gem-Dimethylcyclopropanation of dibenzylideneacetone using triisopropyl sulfoxonium tetrafluoroborate

Abstract

The reaction between dibenzylideneacetone (dba) and triisopropyl sulfoxonium tetrafluoroborate has been reinvestigated. The stereochemistry of the major diasteromeric bis(gem-dimethylcyclopropane) adduct has now been assigned as [(1RS,3RS)-2,2-dimethyl-3-phenylcyclopropyl][(1SR,3SR)-2,2-dimethyl-3-phenylcyclopropyl]methanone, C(23)H(26)O, by X-ray crystallographic studies on a twinned crystal. The asymmetric unit contains two molecules of the adduct, the conformations of which differ in the orientation of the phenyl ring relative to the adjacent cyclopropanated double bond. The carbonyl groups of each adduct are aligned approximately along the a axis and in opposite directions to each other. The molecules pack to give a sinusoidal pattern along the b axis. This is the first acyclic bis(dimethylcyclopropyl) ketone for which an X-ray crystal structure determination has been reported, and is also the first bis-cyclopropanated dba analogue. The knowledge that the major diastereomer has the meso structure (and therefore the confirmation that the minor isomer is the racemate) will prove invaluable in future studies to utilize bis(dimethylcyclopropyl) ketones as reagents, in rearrangement processes, and as potential ligands and ligand precursors in organometallic chemistry.