Capurso Matías, Radivoy Gabriel, Nador Fabiana, Dorn Viviana
Instituto de Química del Sur (INQUISUR-CONICET), Depto. de Química, Universidad Nacional del Sur Av. Alem 1253 B8000CPB Bahía Blanca Argentina
RSC Adv. 2023 Mar 10;13(12):8025-8033. doi: 10.1039/d3ra00169e. eCollection 2023 Mar 8.
Density functional theory (DFT) calculations were applied to describe the hydrothiolation reaction of activated alkynes with thiols bearing a catechol group. The thiol-yne click (TYC) process was efficiently catalysed by a CuNPs/TiO nanocatalyst giving the corresponding -Markovnikov vinyl sulphides with high -stereoselectivity. Based on the experimental results and DFT studies, a plausible reaction mechanism is proposed, which implies the activation of the carbon-carbon triple bond by coordination to the copper centre, followed by a stereoselective (external) nucleophilic attack to give preferentially the -vinyl sulphide isomer. Additionally, experimental and theoretical studies strongly correlate with the proposed synergistic role for the TiO support in the catalytic process.
采用密度泛函理论（DFT）计算来描述活性炔烃与带有儿茶酚基团的硫醇的氢硫基化反应。铜纳米颗粒/二氧化钛（CuNPs/TiO）纳米催化剂能有效催化硫醇-炔点击（TYC）过程，以高立体选择性生成相应的马氏规则乙烯基硫醚。基于实验结果和DFT研究，提出了一种合理的反应机理，该机理表明碳-碳三键通过与铜中心配位而活化，随后进行立体选择性（外部）亲核进攻，优先生成β-乙烯基硫醚异构体。此外，实验和理论研究有力地证明了二氧化钛载体在催化过程中所提出的协同作用。
