Darroudi Mahdieh, Hamzehloueian Mahshid, Sarrafi Yaghoub
Department of Organic Chemistry, Faculty of Chemistry, University of Mazandaran, 47416 Babolsar, Iran.
Department of Chemistry, Jouybar Branch, Islamic Azad University, Jouybar, Iran.
Heliyon. 2021 Feb 2;7(2):e06113. doi: 10.1016/j.heliyon.2021.e06113. eCollection 2021 Feb.
An efficient procedure for the synthesis of novel thiazolidinone triazoles through 32 cycloaddition reactions in the presence of copper(I) species was described, and the molecular mechanism of this 32CA was investigated computationally. Different possible pathways for CA process have been studied to achieve this goal, including pathways for both regioisomers 1,4- and 1,5-triazoles (uncatalyzed, mono-copper, di-copper) and also mono- and di-copper stepwise pathways for 1,4-disubstituted triazole. It was exhibited that the most convenient route in terms of energy barriers includes two copper ions. Based on the calculation, the reaction follows a di-copper stepwise mechanism involving the formation of a six-membered ring and then undergoes a ring contraction to a five-membered ring. The regiochemistry of the reaction was investigated based on local and global reactivity indices of reactants, the transition state stabilities calculation. The electron reorganization along the uncatalyzed one-step mechanism has been investigated by the ELF topological analysis of the bonding changes along with the CA reaction.
描述了一种在铜（I）物种存在下通过3 + 2环加成反应合成新型噻唑烷酮三唑的有效方法，并通过计算研究了该3 + 2环加成反应的分子机理。为实现这一目标，研究了环加成过程的不同可能途径，包括1,4 - 和1,5 - 三唑区域异构体（未催化、单铜、双铜）的途径，以及1,4 - 二取代三唑的单铜和双铜逐步途径。结果表明，就能量壁垒而言，最便捷的途径涉及两个铜离子。基于计算，该反应遵循双铜逐步机理，包括形成一个六元环，然后经历环收缩形成一个五元环。基于反应物的局部和全局反应性指数、过渡态稳定性计算研究了反应的区域化学。通过对环加成反应过程中键变化的电子定域函数拓扑分析，研究了未催化一步机理中的电子重排。
