We report an efficient procedure to carry out palladium-catalyzed Miyaura borylation reactions of (hetero)aromatic halides and triflates in choline chloride (ChCl)-based deep eutectic solvents (DESs). The procedure employs bis(pinacolato)diboron as a boron source and a catalyst prepared in situ from readily available Pd₂(dba)₃ and the phosphine ligand XPhos. Reactions proceed well in different ChCl-based DESs, among which the best results were provided by environmentally friendly and biodegradable mixtures with glycerol and glucose. The reaction tolerates both EDG and EWG substituents on the substrates and can be run on different halides (chloride, bromide, iodide) and pseudohalides (triflate). Furthermore, for several substrates, the catalyst loading can be reduced to 1 mol % Pd (0.5% mol Pd₂(dba)₃) without compromising the reaction yield. Moreover, we show that the Miyaura borylation protocol in DES can be combined with a subsequent Suzuki–Miyaura cross-coupling reaction in a one-pot procedure, allowing access to various biaryl products and demonstrating its synthetic utility by preparing the precursors of two compounds with reported applications in the photovoltaics sector. Finally, two green metrics (E-factor and EcoScale) of the new one-pot procedure in DES were calculated and compared with literature values to assess the potential advantages in terms of waste reduction, safety, and energy consumption.

中文翻译：

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深共晶溶剂中 Pd 催化的 Miyaura 硼化和伸缩硼化/Suzuki-Miyaura 交叉偶联过程

我们报告了一种在氯化胆碱（ChCl）基低共熔溶剂（DES）中进行（杂）芳香族卤化物和三氟甲磺酸酯的钯催化宫浦硼化反应的有效程序。该程序采用双(频哪醇)二硼作为硼源和由容易获得的Pd ₂ (dba) ₃和膦配体XPhos原位制备的催化剂。反应在不同的 ChCl 基 DES 中进行得很好，其中最好的结果是环境友好且可生物降解的甘油和葡萄糖混合物。该反应可耐受底物上的 EDG 和 EWG 取代基，并且可以在不同的卤化物（氯化物、溴化物、碘化物）和拟卤化物（三氟甲磺酸盐）上运行。此外，对于几种底物，催化剂负载量可以减少至1 mol% Pd (0.5% mol Pd ₂ (dba) ₃ )，而不影响反应产率。此外，我们表明，DES 中的 Miyaura 硼化方案可以与随后的 Suzuki-Miyaura 交叉偶联反应在一锅程序中结合，从而获得各种联芳基产物，并通过制备两种化合物的前体来证明其合成实用性报道了在光伏领域的应用。最后，计算了 DES 中新一锅法程序的两个绿色指标（E-factor 和 EcoScale），并与文献值进行比较，以评估其在减少废物、安全性和能源消耗方面的潜在优势。