cis-2,3-Di-tert-butylcyclopropanones

The preparation of the strained cis-2,3-di-tert-butylcyclopropanone 2 from the acyclic compound, α,α′-dibromodineopentyl ketone 1, using a previously reported methodology, is dramatic evidence of both the existence of oxyallyl intermediates in the mechanism of this reaction, and of the integrity with which oxyallyls ring-close to cyclopropanones by a disrotatory route. Because of the bulky cis substituents, cyclopropanone 2 exhibits a number of unusual spectroscopic features (as compared to the trans isomer 5). With the aid of ab initio calculations on 2 and 5, it can be shown that the C2—C3 bond in 2 interacts with the carbonyl π-orbitals, thus causing the carbonyl oxygen to bend 12° out of the plane; this interaction is absent in 5 and the latter has a planar carbonyl group. As with other cyclopropanones, 2 can be photochemically decarbonylated. This process itself appears to be stereospecific even though highly strained alkenes are produced. Cyclopropanone 2 is thermally rearranged to the trans isomer 5 and the kinetics for this are reported; our favoured mechanism involves oxyallyl intermediates. Other reactions of 2 also appear to proceed through these oxyallyl species; for example, alcohols initially add to 2 to give α-alkoxy ends, solutions of 2 enter into very facile diene cycloadditions, and the dimerization of neat 2 also appears to involve these oxyallyl species. Keywords: cyclopropanones, oxyallyl, stereomutation, stereospecific decarbonylation, nonplanar carbonyl.