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

Murphy, Damien Martin ORCID: https://orcid.org/0000-0002-5941-4879, Fallis, Ian Andrew ORCID: https://orcid.org/0000-0001-7361-0182, Carter, Emma ORCID: https://orcid.org/0000-0001-6691-2377, Willock, David James ORCID: https://orcid.org/0000-0002-8893-1090, Landon, J., Van Doorslaer, S. and Vinck, E. 2009. Enantioselective binding of structural epoxide isomers by a chiral vanadyl salen complex: a pulsed EPR, cw-ENDOR and DFT investigation. Physical Chemistry Chemical Physics 11 (31) , pp. 6757-6769. 10.1039/b907807j

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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.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Advanced Research Computing @ Cardiff (ARCCA) Chemistry Cardiff Catalysis Institute (CCI)
Subjects:	Q Science > QD Chemistry
Publisher:	Royal Society of Chemistry
ISSN:	1463-9076
Last Modified:	17 Oct 2022 09:53
URI:	https://orca.cardiff.ac.uk/id/eprint/6075

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