The detail mechanisms of enantioselective Ni-catalyzed reductive coupling of 5-bromide-2-methoxypyridine (R₁) and (1-chloropropyl) benzene (R₂) to form 1,1-diarylalkanes (R, S)-P were studied using Density Functional Theory calculations. The overall catalytic cycles include the following basic steps: the oxidative addition, reduction, radical production, radical addition, reductive elimination and the catalyst regeneration. Our calculated results show that the favored way from the reactant (S)-R₂ to get the products (R, S)-P is Path C (the Ni^I catalyst initially combined with alkyl chloride) where the energy barrier of the rate-determining step is the oxidative addition step with 9.1 kcal/mol (of TS_1b), but the favored path starting from the reactant (R)-R₂ to get the products (R, S)-P is Path A (the Ni^I catalyst initially combined with aryl bromide) or Path B (the Ni° catalyst initially combined with the aryl bromide) where the energy barrier of the rate-determining step is the radical production step with 12.7 kcal/mol (of (R)-TS₂). Our calculated results also indicate that the formation of (R)-P is dominant over the product (S)-P, which meets the experimental results. The ligand effects have also been studied.

使用对映选择性镍催化还原偶联 5-溴-2-甲氧基吡啶 ( R ₁ ) 和 (1-氯丙基) 苯 ( R ₂ )形成 1,1-二芳基烷烃( R, S )-P的详细机理研究密度泛函理论计算。整个催化循环包括以下基本步骤：氧化加成、还原、自由基产生、自由基加成、还原消除和催化剂再生。我们的计算结果表明，从反应物( S )-R ₂获得产物( R, S )-P的有利途径是路径 C（Ni ^I催化剂最初与烷基氯结合），其中限速步骤的能量势垒是氧化加成步骤，具有 9.1 kcal/mol（TS _1b），但从反应物( R )-R ₂开始的有利路径得到产物( R, S )-P是路径 A（Ni ^I催化剂最初与芳基溴化物结合）或路径 B（Ni°催化剂最初与芳基溴化物结合），其中速率决定步骤的能垒是自由基12.7 kcal/mol ( ( R )-TS ₂ )的生产步骤。我们的计算结果还表明( R)-P比乘积( S )-P占优势，符合实验结果。还研究了配体效应。