Cu(I)-Catalyzed Highly Diastereo- and Enantioselective Constructions of Boron/Carbon Vicinal Stereogenic Centers Via Insertion Reaction

The diastereoselective synthesis of boron and carbonvicinal stereogeniccenters is a great challenge in current synthetic chemistry due tothe paucity of efficient synthetic strategies. Herein, a Cu-catalyzeddiastereo- and enantioselective B-H bond insertion reactionof ene-yne-ketones as furyl-carbene precursors has been developedusing chiral bis(oxazolines) (BOX) as the ligand, thus furnishinga series of densely functionalized products (42 examples) bearingboth boron and carbon vicinal stereogenic centers in high enantioselectivityand high diastereoselectivity (up to 99% ee and > 20:1 dr) withgoodyields (up to 98%).