Metal-Free Deoxygenation and Reductive Disilylation of Nitroarenes by Organosilicon Reducing Reagents

被引：32
作者：
Bhattacharjee, Argha [1 ]
Hosoya, Hiromu [1 ]
Ikeda, Hideaki [1 ]
Nishi, Kohei [1 ]
Tsurugi, Hayato [1 ]
Mashima, Kazushi [1 ]
机构：
[1] Osaka Univ, Grad Sch Engn Sci, Dept Chem, 1-3 Machikaneyama Cho, Toyonaka, Osaka 5608531, Japan
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2018年 / 24卷 / 44期
关键词：
azo compounds; cleavage reactions; deoxygenation; nitrogen heterocycles; reduction; AROMATIC NITRO-COMPOUNDS; TRANSFER HYDROGENATION; ALPHA-DEOXYSILYLATION; AMINES; GENERATION; WATER; PHENYLNITRENE; MULTIPLICITY; DERIVATIVES; CHEMISTRY;
D O I：
10.1002/chem.201801972
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A metal-free deoxygenation and reductive disilylation of nitroarenes was achieved using N,N-bis(trimethylsilyl)-4,4'-bipyridinylidene (1) under mild and neutral reaction conditions, and a broad functional group tolerance was possible in this reaction. Mono-deoxygenation, giving a synthetically valuable N,O-bis(trimethylsilyl)phenylhydroxylamine (7a) as a readily available and safe phenylnitrene source from nitrobenzene, and double-deoxygenation, giving N,N-bis(trimethylsilyl)anilines 8, were easily controlled by varying the amounts of 1 and reaction temperature as well as adding dibenzothiophene (DBTP). Reaction of 2-arylnitrobenzenes with 1 resulted in the formation of the corresponding carbazoles 14 via in situ-generated phenylnitrene species derived by thermolysis of N,O-bis(trimethylsilyl)phenylhydroxylamines 7, followed by their subsequent intramolecular C-H insertion. In addition, the intramolecular N-N coupling reaction proceeded in the reduction of 2,2'-dinitrobiphenyl derivatives by 1, giving the corresponding benzo[c]cinnolines.
引用
收藏
页码：11278 / 11282
页数：5
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