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无膦钌配合物催化通过借氢策略合成单烷基化或二烷基化酰肼

Phosphine-Free Ruthenium Complex-Catalyzed Synthesis of Mono- or Dialkylated Acyl Hydrazides via the Borrowing Hydrogen Strategy.

作者信息

Joly Nicolas, Bettoni Léo, Gaillard Sylvain, Poater Albert, Renaud Jean-Luc

机构信息

LCMT, ENSICAEN, UNICAEN, CNRS, Normandie Université, 6 boulevard du Maréchal Juin, 14000 Caen, France.

Departament de Química, Institut de Química Computacional i Catàlisi (IQCC), University of Girona, c/Maria Aurèlia Capmany 69, 17003 Girona, Catalonia, Spain.

出版信息

J Org Chem. 2021 May 7;86(9):6813-6825. doi: 10.1021/acs.joc.1c00654. Epub 2021 Apr 20.

Abstract

Herein, we report a diaminocyclopentadienone ruthenium tricarbonyl complex-catalyzed synthesis of mono- or dialkylated acyl hydrazide compounds using the borrowing hydrogen strategy in the presence of various substituted primary and secondary alcohols as alkylating reagents. Deuterium labeling experiments confirm that the alcohols were the hydride source in this cascade process. Density functional theory (DFT) calculations unveil the origin and the threshold between the mono- and dialkylation.

摘要

在此,我们报道了一种二氨基环戊二烯酮三羰基钌配合物催化的反应,该反应采用借氢策略,以各种取代的伯醇和仲醇作为烷基化试剂,合成单烷基化或二烷基化酰肼化合物。氘标记实验证实,在该串联过程中醇是氢化物的来源。密度泛函理论(DFT)计算揭示了单烷基化和二烷基化之间的起源和界限。

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