Home

Citation: Jia Li, Xiao Hu, Jianchun Wang, Kaige Yu, Shining Geng, Xiangfu Meng. 取代环己酮还原立体选择性的过渡态理论解释[J]. University Chemistry, ;2022, 37(3): 210600. doi: 10.3866/PKU.DXHX202106004 shu

取代环己酮还原立体选择性的过渡态理论解释

Department of Chemistry, Capital Normal University, Beijing 100048, China

Corresponding author: Xiangfu Meng, xfmeng@cnu.edu.cn
Received Date: 3 June 2021

对于取代环已酮还原产物的立体选择性，仅通过还原试剂的动力学条件和生成产物的热力学稳定性进行预测是不准确的，需要考虑反应过程中存在的其他因素。采用过渡态理论可以对取代环已酮还原产物的立体选择性进行更全面、更准确的预测。一方面，还原试剂进攻羰基形成过渡态时，表现出决定立体选择性的空间位阻效应和电子效应；另一方面，反应物优势构象，即形成过渡态时的扭转应变和相对于标准对交叉构象偏转角的大小对产物的立体选择性也不容忽视。本文从过渡态形成过程中所体现的空间位阻、电子效应和构象三方面进行讨论，阐述了取代环已酮还原产物的立体选择性。
- Substituted cyclohexanone,
- Reduction,
- Stereoselectivity,
- Transition state,
- Theoretical explanation
1. [1]
  Donald, C. W. Tetrahedron 1979, 35, 449.
2. [2]
  Eliel, E. L.; Senda, Y. Tetrahedron 1970, 26, 2411.
3. [3]
  Cieplak, A. S. J. Am. Chem. Soc. 1981, 103, 4540.
4. [4]
  Neufeldt, S. R.; Gonzalo, J. O.; Comins, D. L.; Houk, K. N. J. Org. Chem. 2014, 79, 11609.
5. [5]
  Juaristi, E.; Cruz-Sanchez, J. S.; Ramos-Morales, F. R. J. Org. Chem. 1984, 49, 4912.
6. [6]
  Ashby, E. C.; Heinsohn, G. E. J. Org. Chem. 1973, 38, 4343.
7. [7]
  Ashby, E. C.; Laemmle, J. T. Chem. Rev. 1975, 75, 521.
8. [8]
  Eliel, E. L. J. Org. Chem. 1961, 26 (9), 3504.
9. [9]
  Brown, H. C.; Dickason, W. C. J. Am. Chem. Soc. 1970, 92, 709.
10. [10]
  Brown, H. C.; Krishnamurthy, S. J. Am. Chem. Soc. 1972, 94, 7159.
11. [11]
  Krishnamurthy, S.; Brown, H. C. J. Am. Chem. Soc. 1976, 98, 3383.
12. [12]
  Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry; Springer:Boston, MA, USA, 2007; p. 253.
13. [13]
  Wu, Y. D.; Tucker, J. A.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5018.
1. [1]
  Zhi Chai , Huashan Huang , Xukai Shi , Yujing Lan , Zhentao Yuan , Hong Yan . Wittig反应的立体选择性. University Chemistry, 2025, 40(8): 192-201. doi: 10.12461/PKU.DXHX202410046
2. [2]
  Hong Lu , Yidie Zhai , Xingxing Cheng , Yujia Gao , Qing Wei , Hao Wei . Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074
3. [3]
  Jingkun Yu , Xue Yong , Ang Cao , Siyu Lu . Bi-Layer Single Atom Catalysts Boosted Nitrate-to-Ammonia Electroreduction with High Activity and Selectivity. Acta Physico-Chimica Sinica, 2024, 40(6): 2307015-0. doi: 10.3866/PKU.WHXB202307015
4. [4]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
5. [5]
  Baitong Wei , Jinxin Guo , Xigong Liu , Rongxiu Zhu , Lei Liu . Theoretical Study on the Structure, Stability of Hydrocarbon Free Radicals and Selectivity of Alkane Chlorination Reaction. University Chemistry, 2025, 40(3): 402-407. doi: 10.12461/PKU.DXHX202406003
6. [6]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
7. [7]
  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
8. [8]
  Runhua Chen , Qiong Wu , Jingchen Luo , Xiaolong Zu , Shan Zhu , Yongfu Sun . Defective Ultrathin Two-Dimensional Materials for Photo-/Electrocatalytic CO₂ Reduction: Fundamentals and Perspectives. Acta Physico-Chimica Sinica, 2025, 41(3): 2308052-0. doi: 10.3866/PKU.WHXB202308052
9. [9]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
10. [10]
  Yunhao Zhang , Yinuo Wang , Siran Wang , Dazhen Xu . Progress in Selective Construction of Functional Aromatics from Nitrogenous Cycloalkanes. University Chemistry, 2024, 39(11): 136-145. doi: 10.3866/PKU.DXHX202401083
11. [11]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
12. [12]
  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
13. [13]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
14. [14]
  Xiaofeng Zhu , Bingbing Xiao , Jiaxin Su , Shuai Wang , Qingran Zhang , Jun Wang . Transition Metal Oxides/Chalcogenides for Electrochemical Oxygen Reduction into Hydrogen Peroxides. Acta Physico-Chimica Sinica, 2024, 40(12): 2407005-0. doi: 10.3866/PKU.WHXB202407005
15. [15]
  Jiakun BAI , Ting XU , Lu ZHANG , Jiang PENG , Yuqiang LI , Junhui JIA . A red-emitting fluorescent probe with a large Stokes shift for selective detection of hypochlorous acid. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1095-1104. doi: 10.11862/CJIC.20240002
16. [16]
  .
  CCS Chemistry | 超分子活化底物为自由基促进高效选择性光催化氧化
  . CCS Chemistry, 2025, 7(10.31635/ccschem.025.202405229): -.
17. [17]
  Feifei Yang , Wei Zhou , Chaoran Yang , Tianyu Zhang , Yanqiang Huang . Enhanced Methanol Selectivity in CO₂ Hydrogenation by Decoration of K on MoS₂ Catalyst. Acta Physico-Chimica Sinica, 2024, 40(7): 2308017-0. doi: 10.3866/PKU.WHXB202308017
18. [18]
  Jun LUO , Baoshu LIU , Yunchang ZHANG , Bingkai WANG , Beibei GUO , Lan SHE , Tianheng CHEN . Europium(Ⅲ) metal-organic framework as a fluorescent probe for selectively and sensitively sensing Pb²⁺ in aqueous solution. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2438-2444. doi: 10.11862/CJIC.20240240
19. [19]
  Shuhong Xiang , Lv Yang , Yingsheng Xu , Guoxin Cao , Hongjian Zhou . Selective electrosorption of Cs(Ⅰ) from high-salinity radioactive wastewater using CNT-interspersed potassium zinc ferrocyanide electrodes. Acta Physico-Chimica Sinica, 2025, 41(9): 100097-0. doi: 10.1016/j.actphy.2025.100097
20. [20]
  Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu . d-Band Center Regulated O₂ Adsorption on Transition Metal Single Atoms Loaded COF: A DFT Study. Acta Physico-Chimica Sinica, 2024, 40(11): 2407013-0. doi: 10.3866/PKU.WHXB202407013

Get Citation

PDF

XML

Metrics

PDF Downloads(17)
Abstract views(1276)
HTML views(166)

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

Address：Zhongguancun North First Street 2,100190 Beijing, PR China Tel: +86-010-82449177-888

DownLoad: Full-Size Img PowerPoint

Return