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Ligand-Free Ru-Catalyzed Direct sp3 C-H Alkylation of Fluorene Using Alcohols.
The Journal of Organic Chemistry ( IF 3.6 ) Pub Date : 2020-01-14 , DOI: 10.1021/acs.joc.9b02913
Moseen A Shaikh 1 , Sandip G Agalave 1 , Akash S Ubale 1 , Boopathy Gnanaprakasam 1
Affiliation  

The sp3 C-H alkylation of 9H-fluorene using alcohol and a Ru catalyst via the borrowing hydrogen concept has been described. This reaction was catalyzed by the [Ru(p-cymene)Cl2]2 complex (3 mol %) and exhibited a broad reaction scope with different alcohols, allowing primary and secondary alcohols to be employed as nonhazardous and greener alkylating agents with the formation of environmentally benign water as a byproduct. A variety of 9H-fluorene underwent selective and exclusive mono-C9-alkylation with primary alcohols in good to excellent isolated yield (26 examples, 50-92% yield), whereas this reaction with secondary alcohols in the absence of any external oxidants furnished the tetrasubstituted alkene as the major product. Furthermore, a base-mediated C-H hydroxylation of the synthesized 9H-fluorene derivatives afforded 9H-hydroxy-functionalized quaternary fluorene derivatives in excellent yield.

中文翻译:

使用醇的无配体Ru催化的芴直接sp3 CH烷基化。

已经描述了通过借用氢概念使用醇和Ru催化剂使9 H-芴的sp 3 CH烷基化。该反应被[Ru(对-cymene)Cl2] 2络合物(3 mol%)催化,并显示出与不同醇的广泛反应范围,使伯醇和仲醇可用作无害且绿色的烷基化剂,形成了副产品是对环境无害的水。各种9H-芴与伯醇的选择性和排他单C9-烷基化反应具有良好的分离效果(26例,产率为50-92%),而在没有任何外部氧化剂的情况下,与仲醇的反应提供了四取代烯烃为主要产物。此外,
更新日期:2020-01-15
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