UNSPECIFIED. (2002) Enantioselective aziridination using copper complexes of biaryl Schiff bases. JOURNAL OF ORGANIC CHEMISTRY, 67 (10). pp. 3450-3458. ISSN 0022-3263

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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 ([Cu2L2](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.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Journal or Publication Title:	JOURNAL OF ORGANIC CHEMISTRY
Publisher:	AMER CHEMICAL SOC
ISSN:	0022-3263
Date:	17 May 2002
Volume:	67
Number:	10
Number of Pages:	9
Page Range:	pp. 3450-3458
Identification Number:	10.1021/jo025515i
Publication Status:	Published
URI:	http://wrap.warwick.ac.uk/id/eprint/10929

Data sourced from Thomson Reuters' Web of Knowledge

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