Synthesis and Suzuki-Miyaura Cross-Coupling of Enantioenriched Secondary Potassium -Trifluoroboratoamides: Catalytic, Asymmetric Conjugate Addition of Bisboronic Acid and Tetrakis(dimethylamino)diboron to ,-Unsaturated Carbonyl Compounds.

Enantioenriched potassium -trifluoroboratoamides have been synthesized an asymmetric, copper-catalyzed 1,4-addition of tetrahydroxydiboron (BBA) and tetrakis(dimethylamino)diboron to ,-unsaturated amides. These dibora reagents provide access to the desired organotrifluoroborates using effective and atom economical sources of boron. The copper-catalyzed -boration is extended to ,-unsaturated ketones and esters. Desired potassium organotrifluoroborates are synthesized with yields up to 92% and enantiomeric ratios up to 98:2. The enantioenriched potassium -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 S2 mechanism an open transition state.