Enantioselective binding of structural epoxide isomers by a chiral vanadyl salen complex: a pulsed EPR, cw-ENDOR and DFT investigation
文献信息
Damien M. Murphy, Ian A. Fallis, Emma Carter, David J. Willock, James Landon, Sabine Van Doorslaer, Evi Vinck
The mode of chiral interaction between a series of asymmetric epoxides (propylene oxide, butylene oxide, epifluorohydrin and epichlorohydrin) and a chiral vanadyl salen complex, N, N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino-vanadium (IV) oxide, [VO(1)], was investigated by a range of electron magnetic resonance techniques (EPR, ENDOR, HYSCORE) and DFT. Enantiomer discrimination of the weakly bound epoxides by the vanadyl complex was evident by cw-ENDOR. The origin of this discrimination was attributed to a number of factors including H-bonds, steric properties and electrostatic contributions, which collectively control the outcome of the chiral interaction. DFT revealed the role of a key H-bond, formed between the epoxide oxygen atom (Oepoxide) and the methine proton (Hexo) attached to the asymmetric carbon atom of the chiral vanadyl salen complex, thereby providing a direct pathway for stereochemical communication between complex and substrate. These findings reveal the potential importance of weak outer sphere interactions in stereoselectivities of enantioselective homogeneous catalysis.
期刊推荐

NDT & E International

Main Group Chemistry

Acta Metallurgica Sinica-English Letters

Biocatalysis and Biotransformation

Polycyclic Aromatic Compounds

Medicinal Chemistry Research

Bioorganic & Medicinal Chemistry Letters

Journal of the Indian Institute of Science

Critical Reviews in Solid State and Materials Sciences

Journal of Chemical Sciences
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.
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