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题名: Density functional study of the L-proline-catalyzed alpha-aminoxylation of aldehydes reaction: The reaction mechanism and selectivity
作者: Wang, HM;  Yang, CL;  Han, KL
关键词: DFT calculations ;  reaction mechanisms ;  proline ;  aminoxylation
刊名: STRUCTURAL CHEMISTRY
发表日期: 2006-02-01
DOI: 10.1007/s11224-006-9001-9
卷: 17, 期:1, 页:97-104
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Multidisciplinary ;  Chemistry, Physical ;  Crystallography
研究领域[WOS]: Chemistry ;  Crystallography
英文摘要: The reaction mechanism of the L-proline-catalyzed alpha-aminoxylation reaction between aldehyde and nitrosobenzene has been investigated using density functional theory (DFT) calculation. Our calculation results reveal following conclusions [1]. The first step that corresponds to the formation of C-O bond, is the stereocontrolling and rate-determining step [2]. Among four reaction channels, the syn-attack reaction channel is more favorable than that of the anti one, and the TS-ss channel dominates among the four channels for this reaction in the step of C-O bond formation [3]. The intermolecular hydrogen bond between the acidic hydrogen of L-proline and the N atom of the nitrosobenzene in an early stage of the process catalyzes very effectively the C-O bond formation by a large stabilization of the negative charge that is developing at the O atom along the electrophilic attack [4]. The effect of solvent decreases the activation energy, and also, the calculated energy barriers are decrease with the enhancement of dielectric constants for C-O bond formation step. These results are in good agreement with experiment, and allow us to explain the origin of the catalysis and stereoselectivity for L-proline-catalyzed alpha-aminoxylation of aldehyde reaction. The addition of H2O to substituted imine proline, intermolecular proton-transfer steps, and the L-proline elimination process were also studied in this paper.
关键词[WOS]: ASYMMETRIC ALDOL REACTIONS ;  ORGANIC CATALYSIS ;  AMINATION ;  ANTIBODY ;  STRATEGIES ;  RESOLUTION ;  CHEMISTRY ;  1,2-DIOLS ;  ALCOHOLS ;  KETONES
语种: 英语
WOS记录号: WOS:000238173700015
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/140286
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian, Peoples R China
2.Yantai Normal Univ, Dept Phys, Shandong, Peoples R China

Recommended Citation:
Wang, HM,Yang, CL,Han, KL. Density functional study of the L-proline-catalyzed alpha-aminoxylation of aldehydes reaction: The reaction mechanism and selectivity[J]. STRUCTURAL CHEMISTRY,2006,17(1):97-104.
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