Solvolysis of 2-thioxo bridgehead compounds as compared with their 2-oxo homologs: Evidence for marked π-conjugation in 2-thioxo carbocation

Abstract

The solvolysis rate ratios of 2-thioxo bicyclic bridgehead compounds relative to the parent compounds increase with flexibility of the ring system, supporting the propriety of the authors' methodology for evaluation of the enhancement of π-conjugation with increasing skeletal flexibility. On the basis of the fact that no appreciable stabilization due to carbonyl conjugation has been detected by this approach, the carbonyl π-conjugation in tertiary α-carbonyl cations, if present, is too small to be detected experimentally.