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 Cu₃L₂(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 C₂ 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.

中文翻译：

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铜（I）/ Feringa-亚磷酰胺催化Cyclohex-2-en-1-one AlEt ₃ 1,4-加成反应的动力学分析

在Et ₂ O中对AlEt ₃（A）和环己-2-烯-1-一（CX）混合物的ReactIR研究表明，路易斯酸碱复合物CX·A在−40°C时立即形成（K = 12.0 M ^–1，ΔG °_反应= −1.1 kcal摩尔^–1）。衍生自预催化Cu（OAc）₂（最高5 mol％）和（R，S，S）-P（邻萘二甲酸酯）{N（CHMePh）₂ }（Feringa's配体（L）的铜（I）催化剂5 mol％）将CX·A（0.04-0.3 M）转化为其1,4-加成产物烯醇盐（E）在-40°C下2000 s之内。对CX·A，CX和（R）-3-乙基环己酮（P，烯酸酯E的H ⁺猝灭产物）的动力学研究（反应动力学和手性GC）表明，真正的催化剂在最初的300 s内形成，随后逐渐形成。提供82％ee中的P。当[ L ] / [Cu]≤3.5时，该真催化剂以速率定律[Cu] ^1.5 [ L ] ^0.66 [ CX·A ] ¹转化CX·A为E。高于此配体比率，添加的[ L ]配体抑制观察到^-2.5。Cu ₃ L ₂（CX·A）₂化学计量比的速率确定步骤（rds）被证明与速率定律最一致。活性催化剂中烯醇化物的存在最能说明反应的诱导期和分子式为[ E ]≡[ CX·A ]。催化通过两个与C ₂对称相关的基态中间体之间的“穿梭机制”进行。每次转换消耗1当量的CX·A，排出一个分子的E，并形成下一循环所需的新的Cu-Et键。观察到的配体（L）抑制和非线性配体大号上的EE EE效果P深受动力学模型模拟。DFT研究（ωB97X-D/ SRSC）支持CX·A与基态Cu三聚体的协调以及其向E的快速转化。