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The copper-catalyzed addition of bis(pinacolato)diboron to internal alkynes in the presence of methanol generates alkenylboron compounds with high levels of regio- and stereoselectivities. The catalytic efficiency is increased by using monodentate phosphine ligands, especially P(p-tolyl)3 and a range of internal alkynes was borylated in good yields.

Graphical abstract: Highly regio- and stereoselective synthesis of alkenylboronic esters by copper-catalyzed boron additions to disubstituted alkynes

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