*3.2. Description of the Screening Experiments*

A Schlenk tube was successively charged with the catalyst (typically 0.1–0.5 mol.% Pd), CuI (9.5 mg, 5 mol.%; if appropriate), phenylacetylene (102 mg, 1.0 mmol), 4-toluoyl chloride (230 mg, 1.5 mmol) and dodecane (internal standard; 170 mg, 1.0 mmol). The reaction vessel was flushed with nitrogen and sealed. The solvent was introduced (5 mL of pure solvent or 5 mL of a solvent with 697 µL (5 mmol) of triethylamine), and the reaction flask was transferred to a Heidolph Synthesis I parallel reactor pre-heated to the required temperature. Aliquots of the reaction mixture were periodically collected, diluted with saturated aqueous NaHCO<sup>3</sup> and centrifuged at 4000 rpm for 5 min. The organic phase was analyzed by gas chromatography.

During recyclation experiments, the reaction mixture obtained after 2 h at 50 ◦C was diluted with acetone (5 mL) and cooled on ice. A small amount of the liquid phase was separated and used to determine the conversion. The solids were filtered off, washed successively with acetone, methanol (removal of triethylammonium chloride) and acetone again. The filtrate and washings were combined and used to quantify the amount of leached-out metal. The recovered solid was used in the next catalytic experiments.
