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题名: Chirality transition in the epoxidation of (-)-alpha-pinene and successive hydrolysis studied by Raman optical activity and DFT
作者: Qiu, Shi1, 2;  Li, Guanna1, 2;  Liu, Peng1, 2;  Wang, Changhao1, 2;  Feng, Zhaochi1;  Li, Can1
刊名: PHYSICAL CHEMISTRY CHEMICAL PHYSICS
发表日期: 2010
DOI: 10.1039/b919993d
卷: 12, 期:12, 页:3005-3013
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical ;  Physics, Atomic, Molecular & Chemical
研究领域[WOS]: Chemistry ;  Physics
英文摘要: Characterization of the chirality evolution involved in chemical and biochemical reaction processes is extremely important to the understanding of the chiral catalysis mechanism. In this work, the chiral transition from the epoxidation of (-)-alpha-pinene to alpha-pinene oxide and successive hydrolysis to (-)-pinanediol has been studied as an archetype of the asymmetric catalysis by Raman optical activity (ROA) and the DFT calculation. Minor changes of the absolute configuration of the chiral products from (-)-alpha-pinene to (-)-pinanediol lead to the dramatic variation in ROA spectra indicating that the chirality is delocalized in the whole molecule rather than only concentrated on the chiral centers. The oxygen atom of alpha-pinene oxide contributes strong ROA signals while the two hydroxyl groups of (-)-pinanediol give no apparent contribution to the chirality in terms of ROA signals. Isolation of the two symmetric anisotropic invariants shows that the predominant contribution to the ROA signals stems from the electric dipole-magnetic dipole invariant, and the bond polarizability model is indeed found to be a good approximation for molecules composed of entirely axially-symmetric bonds in alpha-pinene oxide and (-)-pinanediol. This study demonstrates the feasibility of using ROA to sensitively monitor the variation of the chirality transition during the chiral reactions either in the chemical or biological system.
关键词[WOS]: CORRELATED MOLECULAR CALCULATIONS ;  GAUSSIAN-BASIS SETS ;  AB-INITIO CALCULATION ;  VIBRATIONAL RAMAN ;  ABSOLUTE-CONFIGURATION ;  ACTIVITY SPECTRA ;  FINE CHEMICALS ;  ALPHA-PINENE ;  SCATTERING ;  DENSITY
语种: 英语
WOS记录号: WOS:000275385700026
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/141836
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 Catalysis, Dalian 116023, Peoples R China
2.Chinese Acad Sci, Grad Univ, Beijing 100049, Peoples R China

Recommended Citation:
Qiu, Shi,Li, Guanna,Liu, Peng,et al. Chirality transition in the epoxidation of (-)-alpha-pinene and successive hydrolysis studied by Raman optical activity and DFT[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2010,12(12):3005-3013.
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