Derese Abera Tadie, Menkir Mengistu Gemech, Wolie Mihret Kendie, Yemam Desalegn Addis
Department of Chemistry, Debre Tabor University Ethiopia
Department of Chemistry, Bahir Dar University Ethiopia.
RSC Adv. 2025 Jan 28;15(4):2862-2873. doi: 10.1039/d4ra06893a. eCollection 2025 Jan 23.
DFT calculations were performed to investigate the possible reaction mechanisms underlying catalyst-free chloroboration reactions of carbonyl compounds with BCl. The interaction between BCl and the C[double bond, length as m-dash]O moiety of carbonyl compounds is a two-step reaction. In the first step, B of BCl forms a bond with the O of the C[double bond, length as m-dash]O moiety, followed by the 1,3-Cl migration process from BCl to the C of the carbonyl group. To indicate the versatility of our synthetic methodology, a catalyst-free chloroboration of a variety of aldehydes and ketones with a broad range of electron-donating and electron-withdrawing groups with BCl was checked. According to DFT results, BCl-induced chloroboration of aldehydes and ketones progressed under a kinetically favorable condition with <20 kcal mol of activation free energy.
进行密度泛函理论（DFT）计算以研究羰基化合物与BCl的无催化剂氯硼化反应背后可能的反应机理。BCl与羰基化合物的C=O部分之间的相互作用是一个两步反应。第一步，BCl中的B与C=O部分的O形成键，随后是1,3-氯从BCl迁移到羰基的C上的过程。为了表明我们合成方法的通用性，我们检查了BCl对各种具有广泛供电子和吸电子基团的醛和酮的无催化剂氯硼化反应。根据DFT结果，BCl诱导的醛和酮的氯硼化反应在动力学有利条件下进行，活化自由能<20 kcal/mol。
