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Gillespie KM, Sanders CJ, O'Shaughnessy P, et al. Enantioselective aziridination using copper complexes of biaryl Schiff bases. J Org Chem. 2002;67(10):3450-8doi: 10.1021/jo025515i.
Gillespie, K. M., Sanders, C. J., O'Shaughnessy, P., Westmoreland, I., Thickitt, C. P., & Scott, P. (2002). Enantioselective aziridination using copper complexes of biaryl Schiff bases. The Journal of organic chemistry, 67(10), 3450-8. https://doi.org/10.1021/jo025515i
Gillespie, Kevin M, et al. "Enantioselective aziridination using copper complexes of biaryl Schiff bases." The Journal of organic chemistry vol. 67,10 (2002): 3450-8. doi: https://doi.org/10.1021/jo025515i
Gillespie KM, Sanders CJ, O'Shaughnessy P, Westmoreland I, Thickitt CP, Scott P. Enantioselective aziridination using copper complexes of biaryl Schiff bases. J Org Chem. 2002 May 17;67(10):3450-8. doi: 10.1021/jo025515i. PMID: 12003558.
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J Org Chem. 2002 May 17;67(10):3450-8. doi: 10.1021/jo025515i.

Enantioselective aziridination using copper complexes of biaryl Schiff bases.

The Journal of organic chemistry

Kevin M Gillespie, Christopher J Sanders, Paul O'Shaughnessy, Ian Westmoreland, Christopher P Thickitt, Peter Scott

Affiliations

  1. Department of Chemistry, The University of Warwick, Coventry CV4 7AL, UK.

PMID: 12003558 DOI: 10.1021/jo025515i

Abstract

Racemic 2,2'-diamino-6,6'-dimethylbiphenyl is resolved using simulated moving bed chromatography, and the absolute configuration of the enantiomers is confirmed via the X-ray crystal structure of a derivative. The diamine is condensed with a range of aldehydes to give bidentate aldimine proligands L. Molecular structures of the complexes formed between L and Cu(I) fall into two classes; bimetallic double helices ([Cu(2)L(2)](2+)) and monometallic ([CuL](+)). The latter are strikingly more efficient in the aziridination of alkenes than are the former in terms of rate, turnover, and enantioselection. In particular, the imine ligand formed from the diamine and 2,6-dichlorobenzaldehyde gives, in combination with Cu(I) or Cu(II), up to 99% ee in the aziridination of 6-acyl-2,2-dimethylchromene and 88-98% ee for a range of cinnamate esters. Styrenic and other alkenes are converted with lower selectivities (5-54%). The catalytic system shows a linear response in product ee to catalyst ee, and the product ee does not vary significantly during the reaction. UV spectrophotometric investigations indicate that conversion of Cu(I) to Cu(II) is not essential for catalysis but that Cu(II) is probably also a competent system.

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