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Volumn 45, Issue 8, 2006, Pages 1292-1297

Highly diastereo- and enantioselective copper-catalyzed domino reduction/aldol reaction of ketones with methyl acrylate

Author keywords

Aldol reaction; Copper; Enantioselectivity; Enolates; Hydrosilylation

Indexed keywords

ALKYLATION; CATALYSTS; CHELATION; COPPER COMPOUNDS; ISOMERS; ORGANIC CHEMICALS; POLYACRYLATES; REACTION KINETICS; REDUCTION; STEREOCHEMISTRY;

EID: 33744913650     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200503791     Document Type: Article
Times cited : (157)

References (124)
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    • For the intramolecular reductive aldol reaction of alkenediones with a stoichiometric amount of the Stryker reagent, see: a) P. Chiu, C. P. Szeto, Z. Geng, K. F. Cheng, Org. Lett. 2001, 3, 1901;
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    • for intramolecular reductive aldol reaction of alkynediones with stoichiometric or catalytic amounts of the Stryker reagent, see: d) P. Chiu, S. K. Leung, Chem. Commun. 2004, 2308;
    • (2004) Chem. Commun. , pp. 2308
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    • for an intramolecular reductive Henry reaction with stoichiometric amounts of the Stryker reagent, see: e) W. K. Chung, P. Chiu, Synlett 2005, 55.
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    • During the preparation of this manuscript, a diastereo- and enantioselective copper-catalyzed intramolecular reductive aldol reaction of α,β-unsaturated esters and ketones was reported: H. W. Lam, P. M. Joensuu, Org. Lett. 2005, 7, 4225.
    • (2005) Org. Lett. , vol.7 , pp. 4225
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    • We have reported the use of copper fluoride-phosphine complexes for the catalytic enantioselective hydrosilylation of aromatic ketones with excellent yields and enantioselectivities: a) S. Sirol, J. Courmarcel, N. Mostefai, O. Riant, Org. Lett. 2001, 3, 4111;
    • (2001) Org. Lett. , vol.3 , pp. 4111
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    • For a special topic on copper-mediated conjugate reductions and reductive aldol reactions with organosilanes as the hydride source, see: P. Chiu, Synthesis 2004, 2943.
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    • note
    • [15c]
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    • [22] for pioneering work on a CuF-(S)-tolbinap-catalyzed enantioselective aldol reaction between silyl dienolate and aldehyde that involved a metalloenolate intermediate, see: a) J. Krüger, E. M. Carreira, J. Am. Chem. Soc. 1998, 120, 837;
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    • note
    • For a CuF-tolbinap-catalyzed enantioselective vinylogous Mukaiyama reaction on aliphatic ketones, see reference [7e].
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    • unpublished results
    • The complex was prepared according to a literature procedure: D. J. Gulliver, W. Levason, M. Webster, Inorg. Chim. Acta 1981, 52, 153; the amount of methanol molecules contained in the complex was determined by single-crystal X-ray crystallographic analysis of the complex (unpublished results).
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    • Gulliver, D.J.1    Levason, W.2    Webster, M.3
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    • note
    • [19c]
  • 112
    • 33746186942 scopus 로고    scopus 로고
    • note
    • A minor trace of phenylethanol (<1%), the product of reduction of acetophenone, was observed by GC analysis.
  • 113
    • 33746186938 scopus 로고    scopus 로고
    • note
    • Under the same conditions, without any additional ligand, 3 (1.25 mol%) gave only 20% conversion after a 2-hour reaction.
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    • note
    • Notably, no effect on the reaction rate was observed when using either preprepared CuOtBu or CuOtBu prepared in situ (from CuCl/NaOtBu); for a report on the salt effect on the rate of the enantioselective 1,4-reduction of β,β-disubstituted nitroalkenes when using both methods of CuOtBu preparation, see reference [20 h].
  • 117
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    • note
    • For example, monodentate Feringa phosphonite, tridentate tBupybox, and tetradentate Trost ligand gave very low activity and/ or no enantioselectivity.
  • 121
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    • These observations are in contrast to those usually made in other processes using taniaphos-derived ligands containing either alkyl or aromatic substituents on phosphorus atoms. Generally, a change from electron-rich aromatic groups to cyclohexyl groups has a negative effect on the enantioselectivity of the process. For some examples, see: a) B. L. Feringa, R. Badorrey, D. Peòa, S. R. Harutyunyan, A. J. Minnaard, Proc. Natl. Acad. Sci. USA 2004, 101, 5834;
    • (2004) Proc. Natl. Acad. Sci. USA , vol.101 , pp. 5834
    • Feringa, B.L.1    Badorrey, R.2    Peòa, D.3    Harutyunyan, S.R.4    Minnaard, A.J.5
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    • note
    • [34a]


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.