Citation: Tianqi Sheng, Xuenan Yang, Zhaoyang Li, Shaoguang Zhang. Understanding structural influences in organoelement compounds through configurational inversion of amines, phosphines, and sulfoxides[J]. University Chemistry, ;2026, 41(7): 415-429. doi: 10.12461/PKU.DXHX202505012 shu

Understanding structural influences in organoelement compounds through configurational inversion of amines, phosphines, and sulfoxides

1.
Tanwei College, Tsinghua University, Beijing 100084, China;
2.
Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, China

Corresponding author: Shaoguang Zhang, sgzhang@mail.tsinghua.edu.cn
Received Date: 8 May 2025
Revised Date: 31 July 2025

Although nitrogen (amine), phosphorus (phosphine), and sulfur (sulfoxide) centered chiral compounds all adopt sp³-hybridized configurations, they demonstrate markedly different energy barriers and rates for configurational inversion, resulting in varying degrees of difficulty in chiral isomer separation. Using these three compound classes as representative examples, this study systematically examines the key factors governing inversion barriers. The analysis reveals that the fundamental distinction originates from the inherent properties of the central atoms, thereby illustrating the foundational principle of organoelement chemistry that “elemental characteristics determine structural and reactivity features”. This work aims to help students develop an electron structure-based approach for understanding structure-reactivity relationships.
- Chiral amines,
- Chiral phosphines,
- Chiral sulfoxides,
- Configuration inversion,
- Organoelement chemistry
1. [1]
2. [2]
  C.D. Montgomery. J. Chem. Educ. 2013, 90(5), 661.
3. [3]
  V. Magné, F. Rammal, G. Berionni, S. Lakhdar, 2.09 Four-Membered Rings With One Phosphorus, Arsenic, Antimony, or Bismuth Atom. In Comprehensive Heterocyclic Chemistry IV, D.S. Black, J. Cossy, C.V. Stevens, Eds., Elsevier: Amsterdam, the Netherlands, 2022, pp. 335–362.
4. [4]
  D.R. Rayner, E.G. Miller, P. Bickart, A.J. Gordon, K. Mislow, J. Am. Chem. Soc. 1966, 88(13), 3138.
5. [5]
6. [6]
7. [7]
  H.V.L. Nguyen, I. Gulaczyk, M. Kręglewski, I. Kleiner, Coord. Chem. Rev. 2021, 436, 213797.
8. [8]
  Y.G. Smeyers, M. Villa, M.L. Senent, J. Mol. Spec. 1996, 177(1), 66.
9. [9]
  L. Nyulászi, L. Soós, G. Keglevich, J. Organomet. Chem. 1998, 566(1), 29.
10. [10]
  J.C. Calderón, A. Herrera, F.W. Heinemann, J. Langer, A. Linden, A. Chelouan, A. Grasruck, R. Añez, T. Clark, R. Dorta, J. Org. Chem. 2023, 88(23), 16144.
11. [11]
  D. de Loera, F. Liu, K.N. Houk, M.A. Garcia-Garibay, J. Org. Chem. 2013, 78(22), 11623.
12. [12]
  A. Igau, H. Grutzmacher, A. Baceiredo, G. Bertrand, J. Am. Chem. Soc. 1988, 110, 6463.
13. [13]
  H. Marom, P.U. Biedermann, I. Agranat, Chirality 2007, 19(7), 559.
14. [14]
  F. Yuste, B.n. Ortiz, J. Israel Pérez, A. Rodrı́guez-Hernández, R. Sánchez-Obregón, F. Walls, J.L. Garcı́a Ruano, Tetrahedron 2002, 58(13), 2613.
15. [15]
  E. Montenegro, A. Moyano, M.A. Pericàs, A. Riera, A. Alvarez-Larena, J.-F. Piniella, Tetrahedron: Asym.1999, 10(3), 457.
16. [16]
  K.D. Reichl, D.H. Ess, A.T. Radosevich, J. Am. Chem. Soc. 2013, 135(25), 9354.
17. [17]
  Z.-L. Wang, H.-S. Hu, L. von Szentpály, H. Stoll, S. Fritzsche, P. Pyykkö, W.H.E. Schwarz, J. Li, Chem. Eur. J. 2020, 26(67), 15558.
18. [18]
  O.I. Kolodiazhnyi, Tetrahedron: Asym. 1998, 9(8), 1279.
19. [19]
  A. Gómez-SanJuan, N. Sotomayor, E. Lete, Beilstein J. Org. Chem. 2013, 9, 313.
20. [20]
  S.-i. Kiyooka, Y. Takeshita, Y. Tanaka, T. Higaki, Y. Wada, Tetrahedron Lett. 2006, 47(26), 4453.
21. [21]
  M.P. Walsh, J.M. Phelps, M.E. Lennon, D.S. Yufit, M.O. Kitching, Nature 2021, 597, 70.
22. [22]
  M.R. Friedfeld, M. Shevlin, J.M. Hoyt, S.W. Krska, M.T. Tudge, P. J. Chirik, Science 2013, 342(6162), 1076.
23. [23]
  H.-G. Cheng, L.-Q. Lu, T. Wang, J.-R. Chen, W.-J. Xiao, Chem. Commun. 2012, 48(45), 5596.
24. [24]
  R. Ma, J. Young, R. Promontorio, F.M. Dannheim, C.C. Pattillo, M.C. White, J. Am. Chem. Soc. 2019, 141(24), 9468.
25. [25]
  C.-H. Yuan, X.-X. Wang, L. Jiao, Angew. Chem. Int. Ed. 2023, 62(17), e202300854.
26. [26]
  Y.-J. Wang, C.-H. Yuan, D.-Z. Chu, L. Jiao, Chem. Sci. 2020, 11(40), 11042.
1. [1]
  Dongheng WANG , Si LI , Shuangquan ZANG . Construction of chiral alkynyl silver chains and modulation of chiral optical properties. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 131-140. doi: 10.11862/CJIC.20240379
2. [2]
  Guilan He , Yaofeng Yuan . 手性二茂铁双膦配体Xyliphos的合成及应用. University Chemistry, 2025, 40(8): 130-137. doi: 10.12461/PKU.DXHX202409122
3. [3]
  Ruiying WANG , Hui WANG , Fenglan CHAI , Zhinan ZUO , Benlai WU . Three-dimensional homochiral Eu(Ⅲ) coordination polymer and its amino acid configuration recognition. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 877-884. doi: 10.11862/CJIC.20250052
4. [4]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, 2024, 39(11): 158-173. doi: 10.12461/PKU.DXHX202403106
5. [5]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
6. [6]
  Qiuting Zhang , Fan Wu , Jin Liu , Zian Lin . Chromatographic Stationary Phase and Chiral Separation Using Frame Materials. University Chemistry, 2025, 40(4): 291-298. doi: 10.12461/PKU.DXHX202405174
7. [7]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, 2024, 39(5): 209-217. doi: 10.3866/PKU.DXHX202311024
8. [8]
  Qi Liang , Xinxin Wang , Xinmiao Zhao , Mohan Yu , Yue Sun . 电子圆二色谱结合量子化学计算的氨基酸手性解析——介绍一个计算化学综合实验. University Chemistry, 2026, 41(5): 380-390. doi: 10.12461/PKU.DXHX202511096
9. [9]
  Haiying Wang , Andrew C.-H. Sue . How to Visually Identify Homochiral Crystals. University Chemistry, 2024, 39(3): 78-85. doi: 10.3866/PKU.DXHX202309004
10. [10]
  Keying Qu , Jie Li , Ziqiu Lai , Kai Chen . Unveiling the Mystery of Chirality from Tartaric Acid. University Chemistry, 2024, 39(9): 369-378. doi: 10.12461/PKU.DXHX202310091
11. [11]
  Ke QIAO , Yanlin LI , Shengli HUANG , Guoyu YANG . Advancements in asymmetric catalysis employing chiral iridium (ruthenium) complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2091-2104. doi: 10.11862/CJIC.20240265
12. [12]
  Xinhe Wu , Chang Cheng . Chiral COF-based S-scheme heterojunction for spin-polarized photocatalytic hydrogen evolution. Acta Physico-Chimica Sinica, 2026, 42(9): 100303-0. doi: 10.1016/j.actphy.2026.100303
13. [13]
  Tingyu Zhu , Hui Zhang , Wenwei Zhang . Exploration and Practice of Ideological and Political Education in the Course of Experiments on Chemical Functional Molecules: Synthesis and Catalytic Performance Study of Chiral Mn(III)Cl-Salen Complex. University Chemistry, 2024, 39(4): 75-80. doi: 10.3866/PKU.DXHX202311011
14. [14]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . 基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
15. [15]
  Conghao Shi , Ranran Wang , Juli Jiang , Leyong Wang . The Illustration on Stereoisomers of Macrocycles Containing Multiple Chiral Centers via Tröger Base-based Macrocycles. University Chemistry, 2024, 39(7): 394-397. doi: 10.3866/PKU.DXHX202311034
16. [16]
  Runjie Li , Hang Liu , Xisheng Wang , Wanqun Zhang , Wanqun Hu , Kaiping Yang , Qiang Zhou , Si Liu , Pingping Zhu , Wei Shao . 氨基酸的衍生及手性气相色谱分离创新实验. University Chemistry, 2025, 40(6): 286-295. doi: 10.12461/PKU.DXHX202407059
17. [17]
  Yinuo Wang , Siran Wang , Yilong Zhao , Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063
18. [18]
  Dawei Zhang , Yuqian Zhao , Mingyu Jiao , Yan Wang . Cultivation of Students’ Critical Thinking in the Practice of Ideological and Political in Organic Chemistry Courses: Taking the Discrimination and Analysis of Chemical Rumors as Examples. University Chemistry, 2025, 40(4): 181-188. doi: 10.12461/PKU.DXHX202405211
19. [19]
  Shuhui Li , Rongxiuyuan Huang , Yingming Pan . Electrochemical Synthesis of 2,5-Diphenyl-1,3,4-Oxadiazole: A Recommended Comprehensive Organic Chemistry Experiment. University Chemistry, 2025, 40(5): 357-365. doi: 10.12461/PKU.DXHX202407028
20. [20]
  Fei Xie , Shichong Yu , Ting Wang , Yongsheng Jin , Dazhi Zhang , Yumeng Hao . Practice and Exploration of O-PIRTAS Flipped Classroom in Organic Chemistry Course. University Chemistry, 2024, 39(4): 238-243. doi: 10.3866/PKU.DXHX202310055

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(96)
HTML views(22)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142