刘有成
自由基化学,单电子转移反应,辅酶NADH模型氢转移反应机理等。
个性化签名
- 姓名:刘有成
- 目前身份:
- 担任导师情况:
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学术头衔:
博士生导师, 中国科学院院士
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学科领域:
有机化学
- 研究兴趣:自由基化学,单电子转移反应,辅酶NADH模型氢转移反应机理等。
刘有成 有机化学家,中国科学院院士
1920年11月6日出生,安徽省舒城县人。
1942年毕业于中央大学。
1945年获奖学金赴英国留学,1948年由利兹大学取得有机化学专业哲学博士学位,随后赴美国西北大学从事博士后研究,1951年到芝加哥大学师从M.S.Kharasch教授任博士后研究员。
1954年由美国回国。1955年到兰州大学工作,历任化学系教授、系主任、系名誉主任、校学术委员会主任。1987年应国家教委聘任兰州大学应用有机化学国家重点实验室主任兼学术委员会主任。
1994年起任中国科学技术大学教授。 曾任国务院学位委员会第二届、第三届学科评议组成员。
1980年当选中国科学院院士(学部委员)。
是第六届全国人民代表大会代表。
研究领域:自由基化学,单电子转移反应,辅酶NADH模型氢转移反应机理等。
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11
【期刊论文】Asymmetric reduction of 2-bromo-1-phenylethylidenemalononitrile with chiral NAD (P) Hmodels
刘有成, Jing Li, a, You-Cheng Liu a, c, * and Jin-Gen Deng b
Tetrahedron: Asymmetry 10 (1999) 4343-4347,-0001,():
-1年11月30日
Reduction of 2-bromo-1-phenylethylidenemalononitrile 1 with the chiral NAD (P) Hmodel (SS)-1-benzyl- 3-(p-tolylsulfinyl)-1, 4-dihydropyridine 2 gives the cyclopropane ring product (S)-2-phenylcyclopropane-1, 1-dicarbonitrile 3 with 54.5% enantiomeric purity.
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刘有成, Hua-Jian Xu, a, Dan-Mei Dai, You-Cheng Liu, b, *, Jing Li, Shi-Wei Luo a and Yun-Dong Wu c
Tetrahedron Letters 46 (2005) 5739-5742,-0001,():
-1年11月30日
The reaction of 1-benzyl-1,4-dihydronicotinamide with a series of 1,1-di-p-substituted-phenyl-2,2-dinitroethylenes in oxygen-saturated acetonitrile produced various amounts of the corresponding ethanes and diaryl ketones according to the electronic structure of the substituent groups indicating a spectrum of intermediate mechanism between polar mechanism and SET mechanism.
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刘有成, Hongyi Wang, a, b, *, Danmei Dai, Youcheng Liu a, * and Qingxiang Guo a
Tetrahedron Letters 43 (2002) 7527-7530,-0001,():
-1年11月30日
A series of compounds, o-bromomethylbenzylidene-malononitrile (1), dimethyl o-bromomethyl-benzylidenemalonate (2) and methyl ∞-cyano-o-bromomethylcinnamate (3) were reduced in the dark and under irradiation by an NAD(P)H model, 1-benzyl-1,4-dihydronicotinamide (BNAH). Two different mechanisms were found, i.e. one-step hydride transfer (polar pathway) and multi-step sequence initiated by single electron transfer (SET pathway). The effect of electron-withdrawing groups on the reactivity of the substrates were discussed in terms of Hammett substituent constants, 13C NMR chemical shift values and cyclic voltammetric redox potentials, and their correlations.
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刘有成, Hong Jiang, a, You-Cheng Liu, *a, Jing Li, Guan-Wu Wang, Yun-Dong Wu, b, Quan-Ming Wang c and Thomas C.W. Mak*c
CHEM. COMMUN., 2002, 882-883,-0001,():
-1年11月30日
9-Fluorenylidenemalononitrile reacts with 10-methyl- 9,10-dihydroacridine in deaerated acetonitrile under irradiation with λ>320nm to give a coupling product 9-dicyanomethyl-9-(10A-methyl-9A-cridinyl)fluorene, characterized by X-ray crystallographic, MS and NMR analyses.
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刘有成, You-Cheng Liu*, , Bin Li, and Qing-Xiang Guo
PHYSICAL REVIEW E VOLUME 48, NUMBER 1 JULY 1993,-0001,():
-1年11月30日
The reduction of 2 bromo-1 (p-X-phenylethylidenemahmonitrile (X-BPM: X=H, F, C1, Br, CN) by ADHmodels BNAH and AcrH2 has been investigated. Based on product analysis, kinetic isotope effect, and free energy relationship, a direct hydride transfer and an electron transfer hydrogen abstraction mechanism is proposed, respectively.
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【期刊论文】Novel photoinduced aromatization of Hantzsch 1,4-dihydropyridines
刘有成, Mei-Zhong Jin, Li Yang, Long-Min Wu, You-Cheng Liu and Zhong-Li Liu*
Chem. Commun., 1998, 2451-2452,-0001,():
-1年11月30日
4-Alkyl- and/or aryl-1,4-dihydro-2,6-dimethylpyridine- 3,5-dicarboxylates (Hantzsch 1,4-dihydropyridines) are quantitatively oxidized to the corresponding pyridine derivatives by irradiation in CCl4 via a photoinduced electron transfer mechanism. in CCl4
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刘有成, Bin Li a, You-Cheng Liu a, b, *, Qing-Xiang Guo a
Journal of Photochemistry and Photobiology A: Chemistry 103 (1997) 101-104,-0001,():
-1年11月30日
2-Bromo-l-phenylethylidenemalonic ester reacts with l-benzyl-1,4-dihydronicotinamide (BNAH) in acetonitrile under illumination at λ>320nm to give three debrominated products: an a,β-unsaturated ester, aβ,γ-unsaturated ester and a dimer. In the presence of magnesium ion, the β,γ-unsaturated ester is formed exclusively. Using deuterated BNAH-4,4-d2 as reagent and spin-trapping technique for monitoring reactive intermediate, it has been shown that the reaction proceeds via two different mechanistic pathways: e-transfer-debromination-H abstraction or dimerization for the formation of the a,β-unsaturated ester and the dimer, and e-transfer-debromination-e-transfet-H+transfer for the formation of the β,-i,-unsaturated ester.
Photoindueed reaction, Spin-trapping technique, Magnesium (, Ⅱ), ions
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刘有成, You-Cheng Liu, *a, b, Hong-Yi Wang, Qing-Chuan Yang c and Thomas C.W. Mak†c
J. Chem. Soc., Perkin Trans. 2, 2000, 649-653,-0001,():
-1年11月30日
The mechanism of reduction of 1,1-diphenyl-2,2-dinitroethylene (DPDN) by 1-benzyl-1,4-dihydronicotinamide (BNAH) in acetonitrile has been investigated. Based on product analysis, isotopic tracing and electrochemical analysis, the reaction takes place by a hydride transfer mechanism giving 1,1-diphenyl-2,2-dinitroethane (DPDNH). Single crystal X-ray analysis shows that DPDN conforms to idealized C2 symmetry, but steric repulsions between the bulky substituents result in an appreciable twist about the central bond, such that the phenyl rings make a dihedral angle of 77.7 and the planar C-NO2 fragments make a dihedral angle of 68.5. A small kinetic H/D isotope effect was obtained, that we propose is due to steric hindrance. Reaction in oxygen-saturated acetonitrile produced DPDNH and benzophenone in the ratio of 59.2: 22.0 as the final products with a total yield of 68.6% by GC. Control experiments were performed, by stirring a solution of DPDN or DPDNH alone in oxygen-saturated acetonitrile, or by stirring a solution of DPDN or DPDNH alone in aqueous acetonitrile containing a small amount of hydrochloric acid or in acetonitrile containing triethylamine. These produced no benzophenone. The results clearly indicate the trapping of a radical species by oxygen in the reaction. A curve-crossing model for the reaction projects that the transition state has partial diradical and partial covalent bonding character. As DPDN has a low-lying π* orbital (LUMO), the radical anion DPDN is a stabilized radical. It is known that the reaction of alkyl and benzyl radicals with oxygen is exothermic with a rate close to the diffusion-controlled limit. Thus, with use of More O'Ferrall's two-dimensional potential energy diagram, the results are rationalized by a mechanistic change induced by steric hindrance so that the transition state collapses in two directions leading to the formation of DPDNH (polar pathway) and benzophenone (ET pathway), respectively.
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刘有成, Xiao-Qing Zhu*, †, ‡ and You-Cheng Liu†
J. Org. Chem., Vol. 63, No.9, 1998-2787,-0001,():
-1年11月30日
Carbanions as a class of very important intermediates in many organic and bioorganic reactions have been extensively studied and continue to be of interest. Generally, two methods are used in the preparation of carbanions, i.e., (1) addition of a nucleophile with a negative charge to unsaturated neutral species (precursors) and (2) removal of a group with a positive charge (e.g., proton) from neutral saturated substrates (the other precursors).1 For 9-(dicyanomethyl) fluorenide carbanion (1) as a thermodynamically unfavorable anion, 9-fluorenylidenemalononitrile (3) and 9-luorenylmalononitrile (4) would be its two typical precursors. In fact, the former only gave 9-fluorenylmalononitrile carbanion (2) rather than anion 1 by addition of a hydride (from LiAlH4 as an example), 2 and the latter by removal of a proton also gave sole anion 2,2 which were rationalized by the much larger thermodynamic stability of 2 than that of 1 (pKa=22 for fluorene and pKa) 11 for dicyanomethane in DMSO).3,4 In this paper, we wish to report the first example of the generation of carbanion 1 by a hydride transfer from 1-benzyl-1,4-dihydronicotinamide (BNAH) to compound 3 in dry CH3CN.
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刘有成, Jing Li, a, You-Cheng Liu, c, *, Jin-Gen Deng, b, Xing-Zhu Li, Xing Cuib and Zhi Li b
Tetrahedron: Asymmetry 11 (2000) 2677-2682,-0001,():
-1年11月30日
The substituent effects on the asymmetric reduction of 2-L-1-(X-Aryl)ethylidenemalononitrile with chiral NADH model (SS)-1-benzyl-3-(p-tolylsulfinyl)-1, 4-dihydropyridine 1 have been investigated and a tentative transition state for the reaction is proposed.
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