*3.3. General Procedure B: One-Pot CHB*/*Sonogashira Reaction*

In a glove box, (Ind)Ir(cod) (8 mg, 0.02 mmol, 2 mol % Ir), dmpe (3 mg, 0.02 mmol, 2 mol %), HBpin (256 mg, 2.0 mmol, 2 equiv), and aryl bromide (1.0 mmol, 1 equiv) were transferred into a Schlenk flask equipped with a magnetic stirring bar. The flask was stoppered, removed from the glove box, and stirred at 150 ◦C until the borylation was judged completely by GC-FID/MS. The reaction mixture was allowed to cool to room temperature and subsequently placed under high vacuum for 1–2 h. The Schlenk flask was brought into the dry box and 1,4-diazabicyclo[2.2.2]octane [DABCO] (225 mg, 2.0 mmol, 2 equiv), allylpalladium chloride dimer (9 mg, 0.025 mmol, 2.5 mol %), P*t-*Bu3 (20 mg, 0.1 mmol, 10 mol %), alkyne (1.1–1.3 mmol, 1.1–1.3 equiv) and acetonitrile (3 mL) were added [50]. The flask was then stoppered and stirred at room temperature until the Sonogashira coupling was judged completely by GC-FID. After completion, 10 mL of water were added to the reaction mixture. The reaction mixture was extracted with ether (10 mL × 3). The combined ether

extractions were washed with brine (10 mL), followed by water (10 mL), dried over MgSO4 before being concentrated under reduced pressure on a rotary evaporator. The crude material was then subjected to column chromatography.
