Key Role of Water in Copper‐ and Base‐free Sonogashira Coupling in Ethanol with [{Pd(μ‐OH)Cl(IPr)}2] as a Highly Effective Precatalyst

Abstract

AbstractAryl bromides and 4‐chlorotoluene as an example aryl chloride in the presence of N‐heterocyclic carbene (NHC) palladium hydroxo dimers of the type [{Pd(μ‐OH)Cl(NHC)}2] (where NHC=IPr, SIPr, IMes, SIMes) undergo an efficient and selective Sonogashira cross‐coupling with (hetero)arylacetylenes. The procedure allows the high‐throughput and selective synthesis of a broad spectrum of 1,2‐diarylacetylenes using 10 ppm of [{Pd(μ‐OH)Cl(IPr)}2] as precatalyst. For the coupling of 4‐chlorotoluene with phenylacetylene, TON=560000 was achieved. Hydrogen chloride was observed as a product of the Sonogashira cross‐coupling reaction. The formation of the active Pd(0) from the Pd(II) complex was found to proceed via ethanol oxidation. Mechanistic studies showed that water plays a key role in the reaction.