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锰催化醇和脒的多组分嘧啶合成。

Manganese-Catalyzed Multicomponent Synthesis of Pyrimidines from Alcohols and Amidines.

机构信息

Anorganische Chemie II-Katalysatordesign, Universität Bayreuth, 95447, Bayreuth, Germany.

出版信息

Angew Chem Int Ed Engl. 2017 Feb 1;56(6):1663-1666. doi: 10.1002/anie.201611318. Epub 2017 Jan 12.

Abstract

The development of catalytic reactions for synthesizing different compounds from alcohols to save fossil carbon feedstock and reduce CO emissions is of high importance. Replacing rare noble metals with abundantly available 3d metals is equally important. We report a manganese-complex-catalyzed multicomponent synthesis of pyrimidines from amidines and up to three alcohols. Our reaction proceeds through condensation and dehydrogenation steps, permitting selective C-C and C-N bond formations. β-Alkylation reactions are used to multiply alkylate secondary alcohols with two different primary alcohols to synthesize fully substituted pyrimidines in a one-pot process. Our PN P-Mn-pincer complexes efficiently catalyze this multicomponent process. A comparison of our manganese catalysts with related cobalt catalysts indicates that manganese shows a reactivity similar to that of iridium but not cobalt. This analogy could be used to develop further (de)hydrogenation reactions with manganese complexes.

摘要

开发催化反应,从醇类合成不同的化合物,以节省化石碳原料并减少 CO 排放,这一点非常重要。用丰富的 3d 金属替代稀有贵金属同样重要。我们报告了一种锰配合物催化的从脒和多达三种醇合成嘧啶的多组分反应。我们的反应通过缩合和脱氢步骤进行,允许选择性地形成 C-C 和 C-N 键。β-烷基化反应用于将两种不同的伯醇与仲醇倍增烷基化,以一锅法合成完全取代的嘧啶。我们的 PN P-Mn 夹钳配合物有效地催化了这个多组分过程。将我们的锰催化剂与相关的钴催化剂进行比较表明,锰表现出与铱相似的反应活性,但与钴不同。这种相似性可用于进一步开发锰配合物的(脱氢)反应。

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