Significantly improved method for the Pd-catalyzed coupling of phenols with aryl halides: Understanding ligand effects
Significantly improved method for the Pd-catalyzed coupling of phenols with aryl halides: Understanding ligand effects
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DOI：
10.1002/anie.200601253
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发表时间：
2006-01-01
影响因子：
16.6
通讯作者：
Buchwald, Stephen L.
中科院分区：
文献类型：
--
作者：
Burgos, Carlos H.;Barder, Timothy E.;Buchwald, Stephen L.
通过量子化学（PBE0/def2-TZVPP; DLPNO-CCSD (T)/cc-pVTZ）和小而可靠的多面体低聚硅氧烷（POSS）模型，从理论上探索了一系列与益生元和生命化学起源相关的天体化学相关的催化产物。本文研究了镍中心配合二氧化硅表面催化不饱和C= C键（丙烯）的非均相氢化反应。在两种可能的区域异构体中，支化异丙基氰化物在热力学和动力学上优于线性正丙基氰化物（T= 200 K）。丁腈的形成是基于区域选择过程的，这对生命起源和生命化学有着深远的意义，并与地球表面化学和地球化学有着深刻的联系。
By means of quantum chemistry (PBE0/def2-TZVPP; DLPNO-CCSD (T)/cc-pVTZ) and small, but reliable models of Polyhedral Oligomeric Silsesquioxanes (POSS), an array of astrochemically-relevant catalysis products, related to prebiotic and origin of life chemistry, has been theoretically explored. In this work, the heterogeneous phase hydrocyanation reaction of an unsaturated C= C bond (propene) catalyzed by a Ni center complexed to a silica surface is analyzed. Of the two possible regioisomers, the branched iso-propyl-cyanide is thermodynamically and kinetically preferred over the linear n-propyl-cyanide (T= 200 K). The formation of nitriles based on a regioselective process has profound implications on prebiotic and origin of life chemistry, as well as deep connections to terrestrial surface chemistry and geochemistry.