400yh spectrometer

Four different experimental setups were explored, namely, A, B, C and D. These four procedures were used for liquid and water-miscible nitriles (A), liquid hydrophobic nitriles (B) and solid nitriles (C and D), see Table 1. All setups have been optimized for keeping substrates in solution with as little amount of DMF as possible. For comparison purposes between the different setups, it should be taken into account that, in order to avoid experimental bias (due to the extremely small amount of catalysts it would have been necessary to weigh), a larger amount of catalysts has been used in for setup A-D (0.050 mmol and 0.075 mmol for PdCl₂ and As₂O₃, roughly 1:380 with respect to substrates). At variance, the amount of PdCl₂ and As₂O₃ has been decreased (ratio 1:6,500, see below) in the large-scale setup allowing the calculation of the TON. For the characterization of the obtained products, the NMR spectra were acquired on a JEOL 400 YH spectrometer (resonating frequencies: 400 and 100 MHz for ¹H and ¹³C, respectively). Spectra were recorded at room temperature (25°C ± 2°C) using solvents with a deuteration degree ≥99.8% and calibrated on solvent residual signals. Deuterated solvents were purchased from Deutero GmbH.

All NMR spectra were acquired on a JEOL 400YH spectrometer (resonating frequencies: 400, 160 and 100 MHz for ¹H, ³¹P and ¹³C, respectively). All spectra were recorded at room temperature (25 ± 2 °C) in solvents with a deuteration degree of 99.8% and calibrated on solvent residual signals [21 (link)]. All deuterated solvents were purchased from Deutero.de (https://www.deutero.de/, accessed on 17 December 2022). ¹H, ³¹P and ¹³C characterization spectra were recorded in CDCl₃. Conversely, for performing solution stability studies, a small amount of each compound has been solubilized in 0.25 mL of MeOD-d₄. Subsequently, 0.25 mL of H₂O were added to each sample and the phosphorus signal was monitored up to 72 h for confirming the stability in aqueous media.