Enantioselective binding of structural epoxide isomers by a chiral vanadyl salen complex: a pulsed EPR, cw-ENDOR and DFT investigation

Literature Information

Publication Date 2009-06-25
DOI 10.1039/B907807J
Impact Factor 3.676
Authors

Damien M. Murphy, Ian A. Fallis, Emma Carter, David J. Willock, James Landon, Sabine Van Doorslaer, Evi Vinck


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Abstract

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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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