Scheme 3. Scope of the Three-Step Synthesis of Aryl Nitriles Directly from Sawdusts.

Lignin weight percentages were determined by the Klason lignin method and are based on triplicate results (see Supporting Figure S3 and Table S4). Mass and wt % yields for aryl nitrile products 5 and 6 are given as averages of duplicate reactions and are reported relative to the mass of lignin (see the Supporting Information pp. S12–S15). SO₂F₂ was generated ex situ from SDI (1,1′-sulfonylbis(1H-imidazole)) and potassium fluoride in TFA. The large-scale reaction with noble fir required Pd–XPhos–G4 (6.5 mol %), K₂CO₃ (3.9 equiv), and KCN (2.0 equiv). See the General Procedures section pp. S11–S12 of the SI. Qualitative assessment by ¹H- and ¹³C-NMR indicates a high purity of the respective compounds 5 and 6 after purification by flash column chromatography, however with the co-elution of minute amounts of ethyl-substituted aryl nitriles (see the SI page S12). Purification methods used: Step 1 (filtration through celite, then filtration through silica), Step 2 (filtration through celite), Step 3 (flash column chromatography); see the General Procedures A and B, pp. S11–S12.