Palladium-Catalyzed Carbonylative 1,3-Dialkynylation of Aliphatic Alkenes Enabled by Pyridine-oxazoline Ligand

Abstract

The transition metal catalyzed dialkynylation of alkenes is an attractive strategy to access variable alkynes, which have wild applications in pharmaceuticals and materials science. While documented dialkynylation methods have focused on installing alkynyl groups at 1,1- or 1,2-positions, 1,3-dialkynylation of simple alkenes remained unexplored. Herein, we developed a palladium-catalyzed carbonylative 1,3-dialkynylation strategy that installs two alkynyl groups onto alkenes in a single step, providing efficient access to 1,6-diynes from readily available aliphatic alkenes and carbon monoxide (CO). This protocol operates under mild reaction conditions and exhibits excellent functional group tolerance (34 examples, yields up to 93%), high regioselectivity, and outstanding chemoselectivity. The design of pyridine-oxazoline (PyOx) ligands in combination with EBX reagents plays a pivotal role in modulating both regioselectivity and chemoselectivity. Moreover, the 1,3-dialkynylated products can be further transformed into various value-added compounds through downstream synthetic manipulations.

Keywords

Palladium catalysis / New pyridine-oxazoline ligand / Aliphatic alkene / Carbon monoxide / Carbonylation reaction / Ethynylbenziodoxole / 1,3-Dialkynylation / 1,6-Diynes

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