Markovnikov‐Selective Palladium Catalyst for Carbonylation of Alkynes with Heteroarenes

A new class of palladium catalysts, based on heterocyclic diphosphines, was rationally designed and synthesized. Application of one of these catalysts allows novel Markovnikov‐selective carbonylation of non‐activated alkynes with heteroarenes to give the corresponding branched α,β‐unsaturated ketones in excellent yields (up to 97 %) and regioselectivities (b/l up to 99:1). In addition to heteroarenes, other common nucloephiles (alcohol, phenol, amine, and amide) furnish the desired carbonylation products smoothly in high yields. Cooler Katalysator: Der Ligand L1 [Bis (2‐(diphenylphosphanyl)‐1H‐pyrrol‐1‐yl)methan] ermöglicht eine allgemeine Palladium‐katalysierte Carbonylierung von nichtaktivierten Alkinen mit Heteroarenen. Die Reaktion verläuft glatt und liefert die verzweigten α,β‐ungesättigten Ketone in guten Ausbeuten und oft mit hoher Markownikoff‐Selektivität. b=verzweigt, l=linear.