title: Synthesis and Suzuki-Miyaura Cross-Coupling of Enantioenriched Secondary Potassiumβ-Trifluoroboratoamides: Catalytic, Asymmetric Conjugate Addition of Bisboronic Acid and Tetrakis(dimethylamino)diboron toα,β-Unsaturated Carbonyl Compounds.
abstract: Enantioenriched potassiumβ-trifluoroboratoamides have been synthesizedviaan asymmetric, copper-catalyzed 1,4-addition of tetrahydroxydiboron (BBA) and tetrakis(dimethylamino)diboron toα,β-unsaturated amides. These dibora reagents provide access to the desired organotrifluoroborates using effective and atom economical sources of boron. The copper-catalyzedβ-boration is extended toα,β-unsaturated ketones and esters. Desired potassium organotrifluoroborates are synthesized with yields up to 92% and enantiomeric ratios up to 98:2. The enantioenriched potassiumβ-trifluoroboratoamides are successfully cross-coupled with an array of aryl and heteroaryl chlorides in high yield with complete stereochemical fidelity as the transmetalation proceeds through an SE2 mechanismviaan open transition state.
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, PA 19104-6323.
authors.forename: Gary A
authors.initials: GA
authors.lastname: Molander
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, PA 19104-6323.
authors.forename: Steven R
authors.initials: SR
authors.lastname: Wisniewski
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, PA 19104-6323.
authors.forename: Mona
authors.initials: M
authors.lastname: Hosseini-Sarvari
keywords: Asymmetric Borylation; Catalytic; Potassium Organotrifluoroborate; Stereospecific Suzuki-Miyaura Cross-Coupling; Tetrahydroxydiboron; Tetrakis(dimethylamino)diboron
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