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A study on the reactions of NADH models with electron-deficient alkenes. A probe for the extreme of concerted electron-hydrogen atom transfer mechanism |
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| Authors: | Xin-Qiang Fang Hong Jiang Yao Fu |
| Institution: | a Department of Chemistry, University of Science and Technology of China, Hefei 230026, China b College of Chemistry, Lanzhou University, Lanzhou 730000, China c Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China |
| Abstract: | 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. |
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