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The Acid-Free Cyclopropanol-Minisci Reaction Reveals the Catalytic Role of Silver–Pyridine Complexes
Organic Letters ( IF 5.2 ) Pub Date : 2018-01-19 00:00:00 , DOI: 10.1021/acs.orglett.7b03938
Andrei Nikolaev 1 , Claude Y. Legault 2 , Minhao Zhang 1 , Arturo Orellana 1
Affiliation  

A well-defined homogeneous silver precatalyst can be utilized for the direct C–H functionalization of a wide range of aromatic nitrogen heterocycles with cyclopropanols under acid-free conditions. This reaction can be conducted on gram-scale and with low catalyst loadings (as low as 1%), which is rare for silver-catalyzed Minisci-type reactions. Moreover, reactivity trends, as well as steric and calculated electronic properties of the heterocycles, strongly suggest that silver–heterocycle complexes formed in situ behave as redox active catalysts and as Lewis acid activators of the heterocycle and that the electronic nature of the heterocyclic substrates tunes the reactivity of the resulting complexes.

中文翻译:

无酸环丙醇-Minisci反应揭示了银-吡啶配合物的催化作用

定义明确的均相银预催化剂可用于在无酸条件下用环丙醇直接对各种芳族氮杂环进行C–H直接官能化。该反应可以以克为单位进行,并且催化剂的负载量低(低至1%),这在银催化的Minisci型反应中很少见。此外,反应性趋势以及杂环的空间和电子性质,强烈表明原位形成的银-杂环配合物可作为氧化还原活性催化剂和杂环的路易斯酸活化剂,并且杂环底物的电子性质会发生变化。所得配合物的反应性。
更新日期:2018-01-19
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