Department of Chemistry, Federal University of São Carlos - UFSCar, Rodovia Washington Luís, km 235, SP-310, São Carlos, São Paulo, Brazil, 13565-905.
Institute of Chemistry, University of Campinas (UNICAMP), PO BOX 6154, Campinas, São Paulo CEP 13083-970, Brazil.
Org Biomol Chem. 2022 Aug 3;20(30):6019-6026. doi: 10.1039/d2ob00391k.
Herein, we report a fully detailed mechanistic study involving an organocatalyzed 1,3-dipolar cycloaddition enolate or stabilized vinylogous carbanion intermediates and azide for the synthesis of 1,2,3-triazoles. A detailed investigation of the elementary steps, intermediates, and transition states of the two organocatalyzed metal-free click reactions is supported by DFT calculations and H NMR monitoring experiments, providing detailed profiles for both reaction mechanisms. Distortion-interaction activation-strain (DIAS) analysis was also employed to further elucidate the regioselectivity in both reactions.
在此，我们报告了一项详尽的机制研究，涉及到有机催化的 1,3-偶极环加成烯醇化物或稳定的烯丙基碳负离子中间体与叠氮化物的反应，用于合成 1,2,3-三唑。通过密度泛函理论（DFT）计算和 H NMR 监测实验，对两种无金属有机催化点击反应的基本步骤、中间体和过渡态进行了详细的研究，为两种反应机制提供了详细的概况。扭曲相互作用激活应变（DIAS）分析也被用于进一步阐明两种反应中的区域选择性。
