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Stereoselective Alcohol Silylation by Dehydrogenative Si–O Coupling: Scope, Limitations, and Mechanism of the Cu–H-Catalyzed Non-Enzymatic Kinetic Resolution with Silicon-Stereogenic Silanes

Authors

  • Sebastian Rendler Dr.,

    1. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster (Germany), Fax: (+49) 251-83-36501
    2. Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg im Breisgau (Germany)
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  • Oliver Plefka Dipl.-Chem.,

    1. Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg im Breisgau (Germany)
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  • Betül Karatas Dr.,

    1. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster (Germany), Fax: (+49) 251-83-36501
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  • Gertrud Auer Dr.,

    1. Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg im Breisgau (Germany)
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  • Roland Fröhlich Dr.,

    1. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster (Germany), Fax: (+49) 251-83-36501
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    • X-ray crystal structure analysis.

  • Christian Mück-Lichtenfeld Dr.,

    1. Theoretische Organische Chemie, Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster (Germany)
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  • Stefan Grimme Prof. Dr.,

    1. Theoretische Organische Chemie, Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster (Germany)
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  • Martin Oestreich Prof. Dr.

    1. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster (Germany), Fax: (+49) 251-83-36501
    2. Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg im Breisgau (Germany)
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Abstract

Ligand-stabilized copper(I)–hydride catalyzes the dehydrogenative Si–O coupling of alcohols and silanes—a process that was found to proceed without racemization at the silicon atom if asymmetrically substituted. The present investigation starts from this pivotal observation since silicon-stereogenic silanes are thereby suitable for the reagent-controlled kinetic resolution of racemic alcohols, in which asymmetry at the silicon atom enables discrimination of enantiomeric alcohols. In this full account, we summarize our efforts to systematically examine this unusual strategy of diastereoselective alcohol silylation. Ligand (sufficient reactivity with moderately electron-rich monophosphines), silane (reasonable diastereocontrol with cyclic silanes having a distinct substitution pattern) as well as substrate identification (chelating donor as a requirement) are introductorily described. With these basic data at hand, the substrate scope was defined employing enantiomerically enriched tert-butyl-substituted 1-silatetraline and highly reactive 1-silaindane. The synthetic part is complemented by the determination of the stereochemical course at the silicon atom in the Si–O coupling step followed by its quantum-chemical analysis thus providing a solid mechanistic picture of this remarkable transformation.

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