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Volumn 44, Issue 18, 2005, Pages 2752-2756

Copper-catalyzed enantioselective conjugate addition of Grignard reagents to α,β-unsaturated esters

Author keywords

Asymmetric catalysis; Conjugate addition; Copper; Enantioselectivity; Grignard reaction

Indexed keywords

ADDITION REACTIONS; COMPLEXATION; COPPER; ESTERS;

EID: 18844403662     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200500317     Document Type: Article
Times cited : (128)

References (51)
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    • To date, only a Rh-catalyzed asymmetric conjugate addition of aryl boron reagents to α,β-unsaturated esters has been reported, but the method is intrinsically unsuitable for the direct addition of alkyl groups: a) S. Sakuma, M. Sakai, R. Itooka, N. Miyaura, J. Org. Chem. 2000, 65, 5951-5955;
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    • and references therein
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    • e) see also references [1a] and [1e].
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    • With other alkyl zinc reagents only modest selectivities were observed; see also: A. Alexakis, C. Benhaim, Tetrahedron: Asymmetry 2001, 12, 1151-1157.
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    • note
    • a) For enantioselective additions of Grignard reagents to lactones, see references [14a] (5 mol% catalyst: 47-82% ee) and [4c] (32 mol% catalyst: 76-90% ee).
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    • note
    • A further decrease in the catalyst loading to 0.05 mol% (S/C = 2000:1) still led to 3a with a remarkable 86% ee and 70% conversion (GC-MS).
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    • note
    • 2 in acetonitrile and converted into the dimeric complex 4a by treatment with halogenated solvents. See Supporting Information for the characterization of 4a and 4a′ and further information.
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    • CCDC 261573 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam. ac.uk/data_request/cif.
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    • note
    • Sterically hindered Grignard reagents, such as iPrMgBr, and aryl Grignard reagents, such as PhMgBr, have provided poor results so far. (iPrMgBr: 26% conversion, 12% ee; PhMgBr: 55% conversion, 1% ee.)
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    • note
    • See Supporting Information for details.
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    • note
    • 2 was prepared by the method shown in Scheme 2 and used in these reactions. The same results were obtained when 4b was prepared in situ.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.