Regio‐ and Stereo‐Selective Synthesis of (E)‐β‐Alkenyl Boronates by Phosphene‐Free CuI‐Catalyzed Hydroboration and Carboboration of Alkynes and Access to Allyl‐Vinyl Ethers

Abstract A convenient and operationally trivial protocol to access synthetically versatile vinylboronates through Cu I catalyzed hydroboration and carboboration of alkynes utilizing bis(pinacolato)diboron (B 2 pin 2 ) as the boron precursor in a 1, 10‐phenanthroline (phen) ligand environment is reported. This is a highly efficient and practical method for the synthesis of regio‐ and stereoselective ( E )‐ β ‐vinylboronates from simple aromatic and aliphatic alkynes. These organoboron compounds have further been utilized for the synthesis of allyl‐vinyl ethers, which are potential starting materials for the Claisen rearrangement via an improved Cu II mediated coupling of allyl alcohols and vinylboronates. The vinylboronates were also subjected to Suzuki‐Miyaura cross coupling reaction, allowing access to the corresponding tri‐ and tetra‐substituted alkenes with good isolated yields.