Past exam of the chemistry B course of the University of Cambridge / 2022 / Paper 1 / B2 / c

The new bridge is made by an intramolecular Michael addition. On the cyclohexanone side, the methyl-bearing fused alpha carbon is quaternary and cannot be deprotonated there. triethylamine can instead generate a small equilibrium population of the enolate at the other, methylene alpha carbon. Its carbon attacks the beta carbon of the enone in the seven-membered ring. The enone pi electrons move towards its carbonyl and then onto oxygen, creating the new bridge and a second enolate.

protonation of that enolate at the former methyl-substituted enone alpha carbon restores the left-hand ketone. The initial enone C=C has therefore become a saturated C–C bond while one new transannular C–C bond forms. Both ketones are retained, and the initial two-ring framework becomes a three-ring framework without changing the total index of hydrogen deficiency. The methyl originally at the fused quaternary centre does not migrate; the other methyl ends up on a protonated, formerly unsaturated carbon. A strong-base concentration large enough for quantitative enolate generation is unnecessary for a favourable intramolecular trapping reaction, and neither an aldol dehydration nor a methyl shift is needed.