DFT studies on the mechanism of allylative dearomatization catalyzed by palladium
DFT studies on the mechanism of allylative dearomatization catalyzed by palladium
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DOI：
10.1021/ja063944i
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发表时间：
2006-10-04
影响因子：
15
通讯作者：
Lin, Zhenyang
中科院分区：
文献类型：
--
作者：
Ariafard, Alireza;Lin, Zhenyang
利用 B3LYP 水平的密度泛函理论计算，研究了 Pd 催化的苄基氯与烯丙基三丁基锡的苄基/烯丙基偶联导致苄基脱芳构化的反应机理。计算表明中间体(eta(3)-苄基)(eta(1)-烯丙基)-Pd(PH3)负责形成动力学上有利的脱芳烃产物。通过将 eta(1)-烯丙基配体的 C-3 末端与 (eta(3)-苄基)(eta(1)-烯丙基)Pd(PH3) 中 eta(3)-苄基配体的对位碳偶联，从中间体中还原消除脱芳香族产物。为了进行比较，还检查了各种 C-C 偶联反应途径。
The reaction mechanism of the Pd-catalyzed benzyl/allyl coupling of benzyl chloride with allyltributylstannan, resulting in the dearomatization of the benzyl group, was studied using density functional theory calculations at the B3LYP level. The calculations indicate that the intermediate (eta(3)-benzyl)(eta(1)-allyl)-Pd(PH3) is responsible for the formation of the kinetically favored dearomatic product. Reductive elimination of the dearomatic product from the intermediate occurs by coupling the C-3 terminus of the eta(1)-allyl ligand and the para-carbon of the eta(3)-benzyl ligand in (eta(3)-benzyl)(eta(1)-allyl) Pd(PH3). For comparison, various C-C coupling reaction pathways have also been examined.