基于HMO方法、FMO理论和DFT计算理解Diels-Alder反应的立体专一性、区域选择性和立体选择性

doi:10.3866/PKU.DXHX202303035

Abstract

Abstract:

The Diels Alder (D-A) reaction represents a crucial component of fundamental organic chemistry education and serves as a quintessential example of structural chemistry analyzed via basic principles of chemical sciences. This study explores the Diels-Alder reaction involving 1-methoxy-1,3-butadiene and acrolein, utilizing tools such as the Hückel molecular orbital (HMO) method, frontier molecular orbital (FMO) theory, and quantum chemical calculations. This approach provides detailed quantitative data and intuitive visual illustrations to elucidate the stereospecificity, regioselectivity, and stereoselectivity inherent to this reaction. The findings from this study serve as valuable resources for students, not only enhancing their understanding of D-A reaction properties and principles, but also developing their interest in computational chemistry and augmenting their problem-solving acumen.

Key words: Diels-Alder reaction, Stereospecificity, Regioselectivity, Stereoselectivity, DFT calculations

Weijia Li, Kai Liu, Yixiang Wang, Zhijun Zhang, Yiying Yang, Dongju Zhang. Exploring Stereospecificity, Regioselectivity, and Stereoselectivity in Diels-Alder Reactions: Insights from HMO Method, FMO Theory, and DFT Calculations[J].University Chemistry, 2023, 38(11): 249-255.

Figures/Tables 6

References 19

1	Diels O. ; Alder K. Justus Liebigs Ann. Chem. 1928, 460, 98. doi: 10.1002/jlac.19284600106
2	Diels O. ; Alder K. Ber. Dtsch. Chem. Ges. 1929, 62, 2081. doi: 10.1002/cber.19290620829
3	Diels O. ; Alder K. Ber. Dtsch. Chem. Ges. 1929, 62, 2087. doi: 10.1002/cber.19290620830
4	邢其毅; 裴伟伟; 徐瑞秋; 裴坚. 基础有机化学, 第4版北京: 北京大学出版社, 2016, 433
5	叶向阳; 郭奇珍. 大学化学, 1993, 8 (1), 22.
6	袁耀锋; 王文峰. 大学化学, 2016, 31 (1), 68.
7	周公度; 段连运. 结构化学基础, 第5版北京: 北京大学出版社, 2017, 176
8	李炳瑞. 结构化学, 第2版北京: 高等教育出版社, 2011, 268
9	孙宏伟. 结构化学, 北京: 高等教育出版社, 2016, 152
10	郭用猷; 张冬菊; 刘艳华. 物质结构基本原理, 第3版北京: 高等教育出版社, 2015, 103
11	Fukui K. Acc. Chem. Res. 1971, 4, 57. doi: 10.1021/ar50038a003
12	Grimme S. J. Comput. Chem. 2006, 27, 1787. doi: 10.1002/jcc.20495
13	Huzinaga S. Comput. Phys. Rep. 1985, 2, 281. doi: 10.1016/0167-7977(85)90003-6
14	Cossi M. ; Rega N. ; Scalmani G. ; Barone V. J. Comput. Chem. 2003, 24, 669. doi: 10.1002/jcc.10189
15	Ieritano C. ; Montgomery C. A. ; Goll J. M. ; Chan H. Y. J. Chem. Educ. 2021, 98, 577. doi: 10.1021/acs.jchemed.0c01166
16	Curtiss L. A. ; Raghavachari K. ; Pople J. A. J. Chem. Phys. 1993, 98, 1293. doi: 10.1063/1.464297
17	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 16, Revision A. 03; Gaussian, Inc. : Wallingford, CT, USA, 2016.
18	Lu T. ; Chen Q. Chemistry-Methods 2020, 1, 231.
19	Lu T. ; Chen Q. J. Comput. Chem. 2022, 43, 539. doi: 10.1002/jcc.26812

[1]	Zhi Chai, Huashan Huang, Xukai Shi, Yujing Lan, Zhentao Yuan, Hong Yan. The Stereoselectivity of the Wittig Reactions [J]. University Chemistry, 2025, 40(8): 192-201.
[2]	Yaqin Zheng, Lian Zhuo, Meng Li, Chunying Rong. Enhancing Understanding of the Electronic Effect of Substituents on Benzene Rings Using Quantum Chemistry Calculations [J]. University Chemistry, 2025, 40(3): 193-198.
[3]	Jiabo Huang, Quanxin Li, Zhongyan Cao, Li Dang, Shaofei Ni. Elucidating the Mechanism of Beckmann Rearrangement Reaction Using Quantum Chemical Calculations [J]. University Chemistry, 2025, 40(3): 153-159.
[4]	Hong Lu, Yidie Zhai, Xingxing Cheng, Yujia Gao, Qing Wei, Hao Wei. Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction [J]. University Chemistry, 2024, 39(5): 154-162.
[5]	Shihui Shi, Haoyu Li, Shaojie Han, Yifan Yao, Siqi Liu. Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy [J]. University Chemistry, 2024, 39(5): 336-344.
[6]	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.
[7]	Yiying Yang, Dongju Zhang. Elucidating the Concepts of Thermodynamic Control and Kinetic Control in Chemical Reactions through Theoretical Chemistry Calculations: A Computational Chemistry Experiment on the Diels-Alder Reaction [J]. University Chemistry, 2024, 39(3): 327-335.
[8]	Danqing Wu, Jiajun Liu, Tianyu Li, Dazhen Xu, Zhiwei Miao. Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways [J]. University Chemistry, 2024, 39(11): 146-157.
[9]	Zhen Zhang, Kai Yang, Qiuling Song. Introduction to the Stereoselective Synthesis of Oximes [J]. University Chemistry, 2024, 39(1): 105-110.
[10]	Jiaxin Wang, Zichun Li, Yuanying Dou, Xulang Chen. Synthesis of Triphenylene Derivatives: Introducing the Formation of Benzene Rings into the Experimental Teaching of Organic Chemistry [J]. University Chemistry, 2023, 38(4): 331-335.
[11]	Rongxiu Zhu, Xiaomo Wang, Jinxin Guo, Dongju Zhang. Understanding the Effect of Solvents on the Nucleophilicity of CH₃O⁻/CH₃S⁻ Using Quantum Chemical Calculations [J]. University Chemistry, 2023, 38(2): 271-276.
[12]	Rongxiu Zhu, Jinxin Guo, Yiying Yang, Dongju Zhang. Quantum Chemical Calculation Study of the Mechanism and Migratory Aptitude of the Baeyer-Villiger Rearrangement: Recommending a Research-Oriented Computational Chemistry Experiment [J]. University Chemistry, 2023, 38(10): 258-265.
[13]	Ling Li, Xueyan Zhang, Xiaoman Wang, Jian Ling, Yong Shi. Selective Epoxidation of Carvone [J]. University Chemistry, 2022, 37(5): 2110099-.
[14]	Jia Li, Xiao Hu, Jianchun Wang, Kaige Yu, Shining Geng, Xiangfu Meng. Explanation of the Transition State Theory of the Stereoselectivity of the Reduction of Substituted Cyclohexanone [J]. University Chemistry, 2022, 37(3): 2106004-.
[15]	Xuexiang Ma, Chengbu Liu, Dongju Zhang. Revealing the Stereoselective Rule of Electrocyclic Reactions of Chain Conjugated Polyenes by Performing Quantum Chemical Calculations [J]. University Chemistry, 2022, 37(12): 2112089-0.

Exploring Stereospecificity, Regioselectivity, and Stereoselectivity in Diels-Alder Reactions: Insights from HMO Method, FMO Theory, and DFT Calculations

RichHTML

PDF

Like

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 6

References 19

Related Articles 15

Metrics

Recommended 0