大学化学2024，Vol.39Issue(4)：305-313,9.DOI:10.3866/PKU.DXHX202309101
典型频哪醇重排反应的机理及基团迁移规律的研究
Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions:A Research-Oriented Computational Chemistry Experiment
摘要
Abstract
Pinacol rearrangement is an important topic in undergraduate organic chemistry courses,but students often struggle to fully understand and grasp the rearrangement mechanism,regioselectivity and group migration aptitude.In order to enhance students'comprehension of pinacol rearrangement reactions,we design an experiment that utilizes computational chemistry methods to address organic chemistry problems.Through intuitive visuals and specific data,the experiment clearly demonstrates that substrates capable of forming stable carbocation intermediates primarily undergo stepwise rearrangement mechanisms,while those unable to form stable intermediates undergo concerted rearrangement mechanisms.The computational results validate that the regioselectivity of the reaction depends on the protonation site of the neighboring diol hydroxyl group and the group migration ability,and it unequivocally establishes the order of group migration ability as hydrogen>aromatic>alkyl.Furthermore,a rational explanation for this order is provided from a microscopic perspective.关键词
频哪醇重排/反应机理/迁移能力/密度泛函理论计算Key words
Pinacol rearrangement/Reaction mechanism/Migratory aptitude/DFT calculations分类
社会科学引用本文复制引用
赵容浩,梁一钒,史梦瑶,朱荣秀,张冬菊..典型频哪醇重排反应的机理及基团迁移规律的研究[J].大学化学,2024,39(4):305-313,9.基金项目
山东省本科教学改革研究项目(计算化学在大学基础化学教学中的应用) （计算化学在大学基础化学教学中的应用）
山东大学教学改革项目(2023Y061,2022Y072) （2023Y061,2022Y072）
