Citation: Ronghao Zhao, Yifan Liang, Mengyao Shi, Rongxiu Zhu, Dongju Zhang. Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment[J]. University Chemistry, ;2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101 shu

Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment

School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China

Corresponding author: Rongxiu Zhu, rxzhu@sdu.edu.cn
Received Date: 28 September 2023
Revised Date: 30 October 2023

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.
- Pinacol rearrangement,
- Reaction mechanism,
- Migratory aptitude,
- DFT calculations
1. [1]
2. [2]
3. [3]
4. [4]
  Clayden, J.; Greeves, N.; Warren, S. G. Organic Chemistry, 2nd ed.; Oxford University Press: Oxford, UK, 2012, pp. 945–949.
5. [5]
  Wadie, T.; Alfy, B. S.; Sami, B. A.; Abdul, A. H. Helv. Chim. Acta1972, 55(8), 2802.
6. [6]
  Eric, L.; Chen, G. P.; He, T.; Kapa, P.; Oljan, R. Tetrahedron Lett.2002, 43(12), 2161.
7. [7]
  Ben, M. B.; Clair, J. C. J. Am. Chem. Soc. 1956, 78(17), 4329.
8. [8]
  William, B. S. Tetrahedron 2002, 58(11), 2091.
9. [9]
  Kensuke, N.; Yoshihiro, O. J. Phys. Org. Chem. 1990, 3(11), 737.
10. [10]
  Duncan, J. F.; Lynn, K. R. J. Chem. Soc. 1956, 3519.
11. [11]
  Herlihy, K. P. Aust. J. Chem. 1981, 34, 107.
12. [12]
13. [13]
  Kensuke, N.; Yoshihiro, O. J. Am. Chem. Soc. 1993, 115(20), 9112.
14. [14]
  Itoh, S.; Yamataka, H. J. Phys. Org. Chem.2010, 23(8), 789.
15. [15]
16. [16]
17. [17]
18. [18]
19. [19]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; et al. Gaussian 09, Revision D. 01; Gaussian, Inc.: Wallingford, CT, USA, 2013.
20. [20]
  Dennington, R.; Keith, T.; Millam, J. GaussView, Version 6.; Semichem Inc.: Shawnee, KS, USA, 2016.
21. [21]
  Legault, C. Y. CYLview, 1.0b; Universite de Sherbrooke: Sherbrooke, Canada, 2009.
22. [22]
  Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
23. [23]
  Fukui, K. Acc. Chem. Res.1981, 14(12), 363.
24. [24]
  Tomasi, J.; Mennucci, B.; Cammi, R. Chem. Rev. 2005, 105(8), 2999.
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