Highly Enantioselective Carbonyl-ene Reactions Catalyzed by a Hindered Silyl−Salen−Cobalt Complex

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Abstract

We report here the enantioselective carbonyl-ene reactions of various 1,1-disubstituted and trisubstituted alkenes with ethyl glyoxylate. The reactions are catalyzed by a new Co−salen complex, in which bulky triisobutylsilyl (TIBS) substituents occupy the positions ortho to the phenolic oxygens. This complex catalyzes the reactions under nearly ideal conditionsat room temperature and using catalyst loadings as low as 0.1 mol %and provides the chiral, homoallylic alcohol products in excellent yields, enantioselectivities, and diastereoselectivities.

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This article has been cited by 8 ACS Journal articles (5 most recent appear below).

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  Mechanistic Basis for High Reactivity of (salen)Co–OTs in the Hydrolytic Kinetic Resolution of Terminal Epoxides

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  The Journal of Organic Chemistry2012 Article ASAP

  • Mechanistic Basis for High Reactivity of (salen)Co–OTs in the Hydrolytic Kinetic Resolution of Terminal Epoxides

    Lars P. C. Nielsen, Stephan J. Zuend, David D. Ford, and Eric N. Jacobsen
    The Journal of Organic Chemistry2012 Article ASAP

    The (salen)Co(III)-catalyzed hydrolytic kinetic resolution (HKR) of terminal epoxides is a bimetallic process with a rate controlled by partitioning between a nucleophilic (salen)Co–OH catalyst and a Lewis acidic (salen)Co–X catalyst. The commonly used (...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Solvent Enhancement of Reaction Selectivity: A Unique Property of Cationic Chiral Dirhodium Carboxamidates

  Xiaochen Wang, Carolin Weigl, and Michael P. Doyle
  Journal of the American Chemical Society2011 133 (24), 9572-9579

  • Solvent Enhancement of Reaction Selectivity: A Unique Property of Cationic Chiral Dirhodium Carboxamidates

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    Journal of the American Chemical Society2011 133 (24), 9572-9579

    1,3-Dipolar cycloaddition reactions of nitrones with α,β-unsaturated aldehydes catalyzed by a cationic chiral dirhodium(II,III) carboxamidate with (R)-menthyl (S)-2-oxopyrrolidine-5-carboxylate ligands in toluene increase reaction rates, give optimum ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Ferrosalen and Ferrosalen-Type Ligands: Structural Modulation and Applications in Asymmetric Catalysis

  Xiang Zhang, Rudy L. Luck, and Shiyue Fang
  Organometallics2011 30 (9), 2609-2616

  • Ferrosalen and Ferrosalen-Type Ligands: Structural Modulation and Applications in Asymmetric Catalysis

    Xiang Zhang, Rudy L. Luck, and Shiyue Fang
    Organometallics2011 30 (9), 2609-2616

    Several ferrosalen and ferrosalen-type ligands, 1−10, were prepared and fully characterized. The structure of one of these ligands ligated to Cu(II) was determined by single-crystal X-ray diffraction analysis. In comparison with the parent ligand 1, the ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Random Copolymerization of ε-Caprolactone with Lactide Using a Homosalen−Al Complex

  Nobuyoshi Nomura, Azusa Akita, Ryohei Ishii and Mitsunori Mizuno
  Journal of the American Chemical Society2010 132 (6), 1750-1751

  • Random Copolymerization of ε-Caprolactone with Lactide Using a Homosalen−Al Complex

    Nobuyoshi Nomura, Azusa Akita, Ryohei Ishii and Mitsunori Mizuno
    Journal of the American Chemical Society2010 132 (6), 1750-1751

    The bulky substituents of homosalen complexes decelerate the ring-opening polymerization of racemic lactide (LA). The substituent effects provide the first catalysis for the random copolymerization of ε-caprolactone (CL) with LA (CL/LA = 1:1). The ...

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• 

  Enantioselective Nitroaldol Reaction Catalyzed by Sterically Modified Salen−Chromium Complexes

  Rafał Kowalczyk, Piotr Kwiatkowski, Jacek Skarżewski and Janusz Jurczak
  The Journal of Organic Chemistry2009 74 (2), 753-756

  • Enantioselective Nitroaldol Reaction Catalyzed by Sterically Modified Salen−Chromium Complexes

    Rafał Kowalczyk, Piotr Kwiatkowski, Jacek Skarżewski and Janusz Jurczak
    The Journal of Organic Chemistry2009 74 (2), 753-756

    A group of modified (salen)Cr(III)Cl complexes with bulky benzylic substituents in the 3,3′-position of the salicylidene moiety have been successfully applied for the asymmetric nitroaldol reaction. The readily accessible complex bearing 3-phenylpent-3-...

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