Asymmetric anti-Selective Borylalkylation of Terminal Alkynes by Nickel Catalysis.

Abstract

Selective transformation of alkyne triple bonds to double bonds serves as an efficient platform to construct substituted alkenes. While significant advances have been made in its spatiotemporal regulation, achieving a multicomponent enantioselective reaction that requires multifaceted selectivity issues to be overcome is still uncommon. Here, we report an unprecedented asymmetric anti-stereoselective borylcarbofunctionalization of terminal alkynes by nickel catalysis. The utilization of an inexpensive chiral diamine ligand enables the three-component cross-coupling of terminal alkynes, a diboron reagent, and prochiral alkyl electrophiles with high levels of regio-, stereo-, and enantioselectivities. This reaction provides an efficient protocol to access enantioenriched alkenyl esters bearing an α-stereogenic center, is remarkably practical, and has a broad scope and an outstanding functional group compatibility. In addition, the value of this method has been highlighted in a diversity of follow-up stereoretentive derivatizations and the stereoselective concise synthesis of complex drug molecules.