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首页> 外文期刊>Proceedings of the National Academy of Sciences of the United States of America >OH-Pd(0) interaction as a stabilizing factor in palladium-catalyzed allylic alkylations
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OH-Pd(0) interaction as a stabilizing factor in palladium-catalyzed allylic alkylations

机译：OH-Pd（0）相互作用作为钯催化的烯丙基烷基化中的稳定因子

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摘要

In palladium-catalyzed alkylations of allylic acetates with malonate as nucleophile, catalysts with oxazoline ligands bearing hydroxymethyl substituents in 4-position have been shown by density functional theory computations to undergo a conformational change on nucleophilic attack, which is accompanied by reduction of Pd(II) to Pd(0). The conformations of the Pd(0) complexes were shown to be governed by the presence of a hydrogen bond with the metal center acting as a hydrogen bond acceptor. The conformational change, which is absent in catalysts with O-alkylated analogs, largely affects the enantioselectivity of the catalytic process. This process is a previously uninvestigated example of where this type of weak hydrogen bond has been shown to influence the stereochemistry of a chemical reaction.
机译：在丙二酸乙酸烯丙酯与亲核体的钯催化的烷基化反应中，密度泛函理论计算表明，带有恶唑啉配体在4位带有羟甲基取代基的催化剂在亲核进攻时发生构象变化，并伴随着Pd（II）的减少。 ）至Pd（0）。 Pd（0）配合物的构象表明是由氢键的存在控制的，金属中心充当氢键受体。具有O-烷基化类似物的催化剂中不存在的构象变化极大地影响了催化过程的对映选择性。此过程是以前未曾研究过的示例，其中已证明这种类型的弱氢键会影响化学反应的立体化学。

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