Asymmetric Allylation

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Patrick J. Walsh - One of the best experts on this subject based on the ideXlab platform.

  • Asymmetric Allylation of ketones and subsequent tandem reactions catalyzed by a novel polymer supported titanium binolate complex
    ChemInform, 2014
    Co-Authors: Jagjit S. Yadav, Patrick J. Walsh, Gretchen R. Stanton, Xinyuan Fan, Jerome R. Robinson, Eric J. Schelter, Miquel A. Pericàs
    Abstract:

    The title catalyst allows successful heterogeneous catalysis for the challenging Asymmetric Allylation of a diverse range of ketones.

  • Asymmetric Allylation of Ketones and Subsequent Tandem Reactions Catalyzed by a Novel Polymer-Supported Titanium—BINOLate Complex.
    ChemInform, 2014
    Co-Authors: Jagjit S. Yadav, Patrick J. Walsh, Gretchen R. Stanton, Xinyuan Fan, Jerome R. Robinson, Eric J. Schelter, Miquel A. Pericàs
    Abstract:

    The title catalyst allows successful heterogeneous catalysis for the challenging Asymmetric Allylation of a diverse range of ketones.

  • Asymmetric Allylation of ketones and subsequent tandem reactions catalyzed by a novel polymer supported titanium binolate complex
    Chemistry: A European Journal, 2014
    Co-Authors: Jagjit S. Yadav, Patrick J. Walsh, Gretchen R. Stanton, Xinyuan Fan, Jerome R. Robinson, Eric J. Schelter, Miquel A. Pericàs
    Abstract:

    By using a novel, simple, and convenient synthetic route, enantiopure 6-ethynyl-BINOL (BINOL = 1,1-binaphthol) was synthesized and anchored to an azidomethylpolystyrene resin through a copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction. The polystyrene (PS)-supported BINOL ligand was converted into its diisopropoxytitanium derivative in situ and used as a heterogeneous catalyst in the Asymmetric Allylation of ketones. The catalyst showed good activity and excellent enantioselectivity, typically matching the results obtained in the corresponding homogeneous reaction. The Allylation reaction mixture could be submitted to epoxidation by simple treatment with tert-butyl hydroperoxide (TBHP), and the tandem Asymmetric Allylation epoxidation process led to a highly enantioenriched epoxy alcohol with two adjacent quaternary centers as a single diastereomer. A tandem Asymmetric Allylation/Pauson-Khand reaction was also performed, involving simple treatment of the Allylation reaction mixture with Co2(CO)8/N-methyl morpholine N-oxide. This cascade process resulted in the formation of two diastereomeric tricyclic enones in high yields and enantioselectivities.

  • Asymmetric Allylation of Ketones and Subsequent Tandem Reactions Catalyzed by a Novel Polymer‐Supported Titanium–BINOLate Complex
    Chemistry (Weinheim an der Bergstrasse Germany), 2014
    Co-Authors: Jagjit S. Yadav, Patrick J. Walsh, Gretchen R. Stanton, Xinyuan Fan, Jerome R. Robinson, Eric J. Schelter, Miquel A. Pericàs
    Abstract:

    By using a novel, simple, and convenient synthetic route, enantiopure 6-ethynyl-BINOL (BINOL = 1,1-binaphthol) was synthesized and anchored to an azidomethylpolystyrene resin through a copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction. The polystyrene (PS)-supported BINOL ligand was converted into its diisopropoxytitanium derivative in situ and used as a heterogeneous catalyst in the Asymmetric Allylation of ketones. The catalyst showed good activity and excellent enantioselectivity, typically matching the results obtained in the corresponding homogeneous reaction. The Allylation reaction mixture could be submitted to epoxidation by simple treatment with tert-butyl hydroperoxide (TBHP), and the tandem Asymmetric Allylation epoxidation process led to a highly enantioenriched epoxy alcohol with two adjacent quaternary centers as a single diastereomer. A tandem Asymmetric Allylation/Pauson-Khand reaction was also performed, involving simple treatment of the Allylation reaction mixture with Co2(CO)8/N-methyl morpholine N-oxide. This cascade process resulted in the formation of two diastereomeric tricyclic enones in high yields and enantioselectivities.

  • Highly concentrated catalytic Asymmetric Allylation of ketones.
    Organic letters, 2007
    Co-Authors: Alfred J. Wooten, Jeung Gon Kim, Patrick J. Walsh
    Abstract:

    We report the catalytic Asymmetric Allylation of ketones under highly concentrated reaction conditions with a catalyst generated from titanium tetraisopropoxide and BINOL (1:2 ratio) in the presence of isopropanol. This catalyst promotes the addition of tetraallylstannane to a variety of ketones to produce tertiary homoallylic alcohols in excellent yield (80–99%) with high enantioselectivities (79–95%). The resulting homoallylic alcohols can also be epoxidized in situ using tert-butyl hydroperoxide (TBHP) to afford cyclic epoxy alcohols in high yield (84–87%).

Miquel A. Pericàs - One of the best experts on this subject based on the ideXlab platform.

Yishuang Zhao - One of the best experts on this subject based on the ideXlab platform.

Pablo Barrio - One of the best experts on this subject based on the ideXlab platform.

Santos Fustero - One of the best experts on this subject based on the ideXlab platform.