Construction of vicinal 4°/3°-carbons reductive Cope rearrangement.

Herein reported is a strategy for constructing vicinal 4°/3° carbons reductive Cope rearrangement. Substrates have been designed which exhibit Cope rearrangement kinetic barriers of ∼23 kcal mol with isoenergetic favorability (Δ ∼ 0). These fluxional/shape-shifting molecules can be driven forward by chemoselective reduction to useful polyfunctionalized building blocks.

Selective ring-rearrangement or ring-closing metathesis of bicyclo[3.2.1]octenes.

Explored was the competitive ring-closing metathesis vs. ring-rearrangement metathesis of bicyclo[3.2.