Enantioselective Synthesis of Tertiary β‐Boryl Amides by Conjunctive Cross‐Coupling of Alkenyl Boronates and Carbamoyl Chlorides

Abstract

Synthesis of versatile β tert-boryl amides is accomplished by conjunctive cross-coupling of α-substituted alkenyl boron “ate” complexes and carbamoyl chloride electrophiles. This reaction can be accomplished in an enantioselective fashion using a palladium catalyst in combination with MandyPhos. The addition of water results in enhanced chemoselectivity for the conjunctive coupling product relative to the Suzuki–Miyaura cross-coupling product. Transformations of the reaction products were examined as well as application to the synthesis of (+)-adalinine.