A study on the reactions of NADH models with electron-deficient alkenes. A probe for the extreme of concerted electron-hydrogen atom transfer mechanism

被引：11
作者：
Fang, Xin-Qiang [1 ]
Xu, Hua-Jian
Jiang, Hong [1 ]
Liu, You-Cheng [1 ,2 ]
Fu, Yao [1 ]
Wu, Yun-Dong [3 ]
机构：
[1] Univ Sci & Technol China, Dept Chem, Hefei 230026, Peoples R China
[2] Lanzhou Univ, Coll Chem, Lanzhou 730000, Peoples R China
[3] Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong, Peoples R China
来源：
TETRAHEDRON LETTERS | 2009年 / 50卷 / 03期
基金：
中国国家自然科学基金; 高等学校博士学科点专项科研基金;
关键词：
ASYMMETRIC TRANSFER HYDROGENATION; HYDRIDE-TRANSFER-REACTIONS; ONE-STEP; METAL-FREE; OXIDATION; 1-BENZYL-1,4-DIHYDRONICOTINAMIDE; REDUCTION; MULTISTEP; CATIONS; ANALOGS;
D O I：
10.1016/j.tetlet.2008.10.143
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The reactions of 9-fluorenylidenemalononitrile (FDCN) and 1,1 -diphenyl-2,2-dicyanoethylene (DPCN) with Hantzsch ester (HEH), N-methyl Hantzsch ester (Me-HEH), and 1-benzyl-1,4-dihydronicotinamide (BNAH) in oxygen-saturated acetonitrile have been studied. The aerobic reactions with HEH give solely reduction products. However, reactions with Me-HEH and BNAH not only result in reduction products, but also give varying amounts of oxidation products. The amount of oxidation product appears to be related to the electronic character and bulkiness of reactants. We propose that all these reactions follow a general mechanism of concerted electron-hydrogen atom transfer mechanism. If the electron-transfer complex is very tight, only 'concerted hydride transfer reaction' occurs. However, if the electron-transfer complex is not so tight, oxygen can capture the radicaloid intermediate to result in oxidation products. (C) 2008 Elsevier Ltd. All rights reserved.
引用
收藏
页码：312 / 315
页数：4
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