Abstract
A facile large-scale synthesis of the “push–pull”-substituted ligand bis(diethylamino)(pentafluorophenyl)phosphane is reported. A selenophosphorane as well as complexes with CuI and PdCl2, can be formed almost quantitatively from suitable starting materials. The PdII complex shows a square-planar coordination with significant distortions of the Cl–Pd–Cl moiety in the solid state. In contrast, the phosphane ligand exhibits a large flexibility in the trigonal-planar coordination of the Cu salt, as proven by X-ray crystallography. C–C cross-coupling reactions and 1,3-dipolar cycloadditions have been tested for the PdII and CuI complexes, respectively. Whereas the reactivity of the PdII complex is good at low temperature, the CuI complex reveals remarkable reaction rates at temperatures up to 130 °C. Furthermore, the CuI-catalyzed azide/alkyne 1,3-dipolar cycloaddition was successfully adapted for flow conditions.
Highlights
Over the last decades palladium has achieved a prominent role in catalysis and organic synthesis
Compound 1 was synthesized by the straightforward and cost-efficient reaction of LiC6F5 with ClP(NEt2)2 at low temperature yielding the pure product after distillation (Scheme 1)
We have demonstrated the cost-efficient synthesis of the pentafluorophenyl-substituted aminophosphane ligand 1, which is available for reactions at the phosphorus lone pair
Summary
Over the last decades palladium has achieved a prominent role in catalysis and organic synthesis. Different types of reaction protocols have been developed for the formation of C–C bonds by the use of palladium catalysts.[1] In many cases optimized phosphane ligands play a crucial role in palladium catalysis, be it for electronic or steric reasons.[2,3,4] Mono-, bis- and tris(amino)-substituted phosphanes represent electron-rich ligand systems,[5] which have been investigated for instance in relation to hydrovinylation reactions.[5] Especially (diethylamino)phosphanes have been widely studied with respect to their coordination behavior[6] and their potential in different catalytic reactions.[7,8].
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