Kinetic Resolution of Tertiary Propargylic Alcohols by Enantioselective Cu−H-Catalyzed Si−O Coupling
Jan Seliger
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany
Search for more papers by this authorDr. Xichang Dong
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Martin Oestreich
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany
Search for more papers by this authorJan Seliger
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany
Search for more papers by this authorDr. Xichang Dong
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Martin Oestreich
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany
Search for more papers by this authorGraphical Abstract
Matchmaker: The commercially available precatalyst system MesCu/(R,R)-Ph-BPE couples Ph3SiH with the fast-reacting enantiomer of racemic mixtures of tertiary propargylic alcohols. This non-enzymatic kinetic resolution provides access to synthetically valuable and versatile enantiomerically enriched tertiary propargylic alcohols and the corresponding silyl ethers (see scheme).
Abstract
A broad range of tertiary propargylic alcohols were kinetically resolved by catalyst-controlled enantioselective silylation. This non-enzymatic kinetic resolution is catalyzed by a Cu−H species and makes use of the commercially available precatalyst MesCu/(R,R)-Ph-BPE and a simple hydrosilane as the resolving reagent. Both alkyl,aryl- as well as dialkyl-substituted propargylic alcohols participate, and especially high selectivity factors are achieved when the alkyne terminus carries a TIPS group, which also enables facile post-functionalization in this position (s up to 207).
Supporting Information
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- 19Conversions were determined by GLC analysis using docosane as an internal standard and calculated according to conversion=eeunreacted alcohol/(eesilyl ether+eeunreacted alcohol).
- 20
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