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Volumn 13, Issue 5, 2011, Pages 1068-1071

NHC-catalyzed/titanium(iv)-mediated highly diastereo-and enantioselective dimerization of enals

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; ALKENE; CARBENE; CYCLOPENTANE DERIVATIVE; DRUG DERIVATIVE; LEWIS ACID; METHANE; TITANIUM;

EID: 79952179067     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol103112v     Document Type: Article
Times cited : (76)

References (74)
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  • 28
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  • 29
    • 56549104231 scopus 로고    scopus 로고
    • For a review of NHC-generated homoenolate methodology
    • For a review of NHC-generated homoenolate methodology, see: Nair, V.; Vellalath, S.; Babu, B. P. Chem. Soc. Rev. 2008, 37, 2691-2698
    • (2008) Chem. Soc. Rev. , vol.37 , pp. 2691-2698
    • Nair, V.1    Vellalath, S.2    Babu, B.P.3
  • 32
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    • For the benzoin reaction, the acyl anion generated in situ adds to the starting material benzaldehyde, thereby typically producing dimeric products.
    • For the benzoin reaction, the acyl anion generated in situ adds to the starting material benzaldehyde, thereby typically producing dimeric products.
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    • and references cited therein.
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    • 2.
    • 2.
  • 57
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    • The absolute and relative stereochemistry of compounds 2 was determined by X-ray crystallography of a related derivative (see Supporting Information) and additional assignments made by analogy.
    • The absolute and relative stereochemistry of compounds 2 was determined by X-ray crystallography of a related derivative (see Supporting Information) and additional assignments made by analogy.
  • 58
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    • Increasing the loading of the base at the beginning of the reaction (e.g., 120 mol %) resulted in <100% conversion with an effective stalling of the process.
    • Increasing the loading of the base at the beginning of the reaction (e.g., 120 mol %) resulted in <100% conversion with an effective stalling of the process.
  • 59
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    • The two side products observed in these reactions are; mainly (E)-isopropyl 3-aryl-acrylate (see ref (14)), and the γ-lactone (1,2-addition).
    • The two side products observed in these reactions are; mainly (E)-isopropyl 3-aryl-acrylate (see ref (14)), and the γ-lactone (1,2-addition).
  • 60
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    • For computational studies supporting an NHC homoenolate conjugate addition pathway, For discussion of an alternative benzoin/oxy-Cope pathway, see ref 10
    • For computational studies supporting an NHC homoenolate conjugate addition pathway, see: Domingo, L. R.; Zaragozá, R. J.; Arnó, M. Org. Biomol. Chem. 2010, 8, 4884-4891. For discussion of an alternative benzoin/oxy-Cope pathway, see ref 10
    • (2010) Org. Biomol. Chem. , vol.8 , pp. 4884-4891
    • Domingo, L.R.1    Zaragozá, R.J.2    Arnó, M.3
  • 61
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    • The relative stereochemistry of compound 13 was determined by X-ray crystallography (Advanced Photon Source) of a related derivative (see Supporting Information).
    • The relative stereochemistry of compound 13 was determined by X-ray crystallography (Advanced Photon Source) of a related derivative (see Supporting Information).
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    • The absolute and relative stereochemistry of compound 14 was determined by X-ray crystallography of a related derivative (see Supporting Information).
    • The absolute and relative stereochemistry of compound 14 was determined by X-ray crystallography of a related derivative (see Supporting Information).
  • 68
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    • 1H NMR NOESY experiments (see Supporting Information for details and reference to a related transformation).
    • 1H NMR NOESY experiments (see Supporting Information for details and reference to a related transformation).


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