ReactIR studies of mixtures of AlEt3 (A) and cyclohex-2-en-1-one (CX) in Et2O indicate immediate formation of the Lewis acid–base complex CX·A at −40 °C (K = 12.0 M–1, ΔG°react = −1.1 kcal mol–1). Copper­(I) catalysts, derived from precatalytic Cu­(OAc)2 (up to 5 mol %) and (R,S,S)-P­(binaphtholate)­{N­(CHMePh)2} (Feringa’s ligand (L), up to 5 mol %) convert CX·A (0.04–0.3 M) into its 1,4-addition product enolate (E) within 2000 s at −40 °C. Kinetic studies (ReactIR and chiral GC) of CX·A, CX, and (R)-3-ethylcyclohexanone (P, the H+ quenching product of enolate E) show that the true catalyst is formed in the first 300 s and this subsequently provides P in 82% ee. This true catalyst converts CX·A to E with the rate law [Cu]1.5[L]0.66[CX·A]1 when [L]/[Cu] ≤ 3.5. Above this ligand ratio inhibition by added ligand with order [L]−2.5 is observed. A rate-determining step (rds) of Cu3 L 2(CX·A)2 stoichiometry is shown to be most consistent with the rate law. The presence of the enolate in the active catalyst best accounts for the reaction’s induction period and molecularity as [E] ≡ [CX·A]. Catalysis proceeds through a “shuttling mechanism” between two C 2 symmetry related ground state intermediates. Each turnover consumes 1 equiv of CX·A, expels one molecule of E, and forms the new Cu–Et bond needed for the next cycle. The observed ligand (L) inhibition and a nonlinear ligand L ee effect on the ee of P are well simulated by the kinetic model. DFT studies (ωB97X-D/SRSC) support coordination of CX·A to the groundstate Cu trimer and its rapid conversion to E.