扭曲型酰胺——结构与功能

引用本文: 史雷, 詹梓烨, 余志友. 扭曲型酰胺——结构与功能[J]. 大学化学, 2024, 39(1): 111-118. doi: 10.3866/PKU.DXHX202306039 shu

Citation: Lei Shi, Ziye Zhan, Zhiyou Yu. The Twisted Amides: Structures and Functions[J]. University Chemistry, 2024, 39(1): 111-118. doi: 10.3866/PKU.DXHX202306039 shu

扭曲型酰胺——结构与功能

哈尔滨工业大学(深圳)理学院, 广东深圳 518055

通讯作者: 史雷,Email:lshi@hit.edu.cn

基金项目:
哈尔滨工业大学（深圳）2021年度创新创业教育课程项目（INRP1023）

摘要: 酰胺作为具有独特物理化学性质和生物活性的含氮化合物，其在医药、材料等领域已展现出了广泛的应用前景。与传统酰胺相比，扭曲型酰胺由于其分子内的p–π共轭被不同程度地破坏，致使酰胺平面结构发生不同程度的扭曲，进而呈现出独特的反应活性。扭曲角τ和角锥化参数χ_N是衡量扭曲型酰胺扭曲程度的两个重要指标，τ描述了N―C（O）键的扭曲程度，χ_N则描述了氮原子的角锥化程度。τ = 40°，χ_N = 40°更是其在反应性上区别平面酰胺的关键阈值。本文着重介绍了当τ > 40°，χ_N > 40°时环状扭曲型酰胺和无环扭曲型酰胺的特殊结构与反应性能。

关键词:

English

The Twisted Amides: Structures and Functions

School of Science, Harbin Institute of Technology, Shenzhen 518055, Guangdong Province, China

Corresponding author: Lei Shi, lshi@hit.edu.cn

Received Date: 14 June 2023

Abstract: Amides, as nitrogen-containing compounds with unique physicochemical properties and biological activities, have demonstrated broad application prospects in fields such as medicine and materials. Particularly, compared with the vast majority of traditional amides in which the intramolecular p-π conjugation effects lead to a planar structure, the twisted amides, however, present distortions of the amide bond from planarity, thus resulting conformational and electronic modifications such as amide bond twist and nitrogen pyramidalization. The bond distortion of twisted amide is typically defined by the Winkler-Dunitz distortion parameters twist angle (τ) and pyramidalization parameters (χ_N). The former describes the magnitude of rotation around the N-C(O) bond while the later describes pyramidalization at nitrogen and pyramidalization at carbon. The values of τ=40° and χ_N=40° are considered as threshold values that allow for unique reactivity of the twist amide bond. This article introduces the unique structure and reactivity of these compounds, focusing on cyclic twisted amides and acyclic twisted amides, based on the range of τ > 40° and χ_N > 40°.

Key words:

1. [1]
  Edison, A. S. Nat. Struct. Mol. Biol. 2001, 8, 201.Edison, A. S. Nat. Struct. Mol. Biol. 2001, 8, 201.
2. [2]
  李锋, 卢永辉, 李涛, 夏露, 钱雪琴, 吴文娟, 卢水华. 新发传染病电子杂志, 2017, No. 2, 25.
3. [3]
  周雪, 张悦凤. 医学理论与实践, 2018, 31, 2903.
4. [4]
  李燕红, 张平, 周小勇. 中国皮肤性病学杂志, 2022, 36, 300.
5. [5]
  Bentley, R. J. Chem. Educ. 2004, 81, 1462.Bentley, R. J. Chem. Educ. 2004, 81, 1462.
6. [6]
  Winkler, F. K.; Dunitz, J. D. J. Mol. Biol. 1971, 59, 169.Winkler, F. K.; Dunitz, J. D. J. Mol. Biol. 1971, 59, 169.
7. [7]
  Greenberg, A.; Moore, D. T.; Dubois, T. D. J. Am. Chem. Soc. 1996, 118, 8658.Greenberg, A.; Moore, D. T.; Dubois, T. D. J. Am. Chem. Soc. 1996, 118, 8658.
8. [8]
  Lukeš, R. Collect. Czech. Chem. Commun. 1938, 10, 148.Lukeš, R. Collect. Czech. Chem. Commun. 1938, 10, 148.
9. [9]
  Szostak, M.; Aubé J. Chem. Rev. 2013, 113, 5701.Szostak, M.; Aubé J. Chem. Rev. 2013, 113, 5701.
10. [10]
  Szostak, M.; Aubé J. Org. Biomol. Chem. 2011, 9, 27.Szostak, M.; Aubé J. Org. Biomol. Chem. 2011, 9, 27.
11. [11]
  Somayaji, V.; Brown, R. S. J. Am. Chem. Soc. 1987, 109, 4738.Somayaji, V.; Brown, R. S. J. Am. Chem. Soc. 1987, 109, 4738.
12. [12]
  Tani, K.; Stoltz, B. M. Nature 2006, 441, 731.Tani, K.; Stoltz, B. M. Nature 2006, 441, 731.
13. [13]
  Ly, T.; Krout, M.; Pham, D. K.; Tani, K.; Stoltz, B. M.; Julian, R. R. J. Am. Chem. Soc. 2007, 129, 1864.Ly, T.; Krout, M.; Pham, D. K.; Tani, K.; Stoltz, B. M.; Julian, R. R. J. Am. Chem. Soc. 2007, 129, 1864.
14. [14]
  Kirby, A. J.; Komarov, I. V.; Feeder, N. J. Chem. Soc., Perkin Trans. 2 2001, 522.Kirby, A. J.; Komarov, I. V.; Feeder, N. J. Chem. Soc., Perkin Trans. 2 2001, 522.
15. [15]
  Kirby, A. J.; Komarov, I. V.; Feeder, N. J. Am. Chem. Soc. 1998, 120, 7101.Kirby, A. J.; Komarov, I. V.; Feeder, N. J. Am. Chem. Soc. 1998, 120, 7101.
16. [16]
  Szostak, R.; Aubé, J.; Szostak, M. Chem. Commun. 2015, 51, 6395.Szostak, R.; Aubé, J.; Szostak, M. Chem. Commun. 2015, 51, 6395.
17. [17]
  Szostak, R.; Aubé, J.; Szostak, M. J. Org. Chem. 2015, 80, 7905.Szostak, R.; Aubé, J.; Szostak, M. J. Org. Chem. 2015, 80, 7905.
18. [18]
  Ratmanova, N. K.; Andreev, I. A.; Leontiev, A. V.; Momotova, D.; Novoselov, A. M.; Ivanova, O. A.; Trushkov, I. V. Tetrahedron 2020, 76, 131031.Ratmanova, N. K.; Andreev, I. A.; Leontiev, A. V.; Momotova, D.; Novoselov, A. M.; Ivanova, O. A.; Trushkov, I. V. Tetrahedron 2020, 76, 131031.
19. [19]
  Daly, J. W.; Spande, T. F.; Garraffo, H. M. J. Nat. Prod. 2005, 68, 1556.Daly, J. W.; Spande, T. F.; Garraffo, H. M. J. Nat. Prod. 2005, 68, 1556.
20. [20]
  Meng, G.; Zhang, J.; Szostak, M. Chem. Rev. 2021, 121, 12746.Meng, G.; Zhang, J.; Szostak, M. Chem. Rev. 2021, 121, 12746.
21. [21]
  Yamada, S. J. Org. Chem. 1996, 61, 941.Yamada, S. J. Org. Chem. 1996, 61, 941.
22. [22]
  Yamada, S. Angew. Chem., Int. Ed. 1993, 32, 1083.Yamada, S. Angew. Chem., Int. Ed. 1993, 32, 1083.
23. [23]
  Pace, V.; Holzer, W.; Meng, G.; Shi, S.; Lalancette, R.; Szostak, R.; Szostak, M. Chem. Eur. J. 2016, 22, 14494.Pace, V.; Holzer, W.; Meng, G.; Shi, S.; Lalancette, R.; Szostak, R.; Szostak, M. Chem. Eur. J. 2016, 22, 14494.
24. [24]
  Otani, Y.; Nagae, O.; Naruse, Y.; Inagaki, S.; Ohno, M.; Yamaguchi, K.; Yamamoto, G.; Uchiyama, M.; Ohwada, T. J. Am. Chem. Soc. 2003, 125, 15191.Otani, Y.; Nagae, O.; Naruse, Y.; Inagaki, S.; Ohno, M.; Yamaguchi, K.; Yamamoto, G.; Uchiyama, M.; Ohwada, T. J. Am. Chem. Soc. 2003, 125, 15191.
25. [25]
  Otani, Y.; Park, S.; Ohwada, T. Chirality 2020, 32, 790.Otani, Y.; Park, S.; Ohwada, T. Chirality 2020, 32, 790.
26. [26]
  Takezawa, H.; Shitozawa, K.; Fujita, M. Nat. Chem. 2020, 12, 574.Takezawa, H.; Shitozawa, K.; Fujita, M. Nat. Chem. 2020, 12, 574.
27. [27]
  Kirby, A. J.; Komarov, I. V.; Feeder, N. J. Chem. Soc., Perkin Trans. 2 2001, 522.Kirby, A. J.; Komarov, I. V.; Feeder, N. J. Chem. Soc., Perkin Trans. 2 2001, 522.
28. [28]
  Kirby, A. J.; Komarov, I. V.; Feeder, N. J. Am. Chem. Soc. 1998, 120, 7101.Kirby, A. J.; Komarov, I. V.; Feeder, N. J. Am. Chem. Soc. 1998, 120, 7101.
29. [29]
  Szostak, M.; Yao, L.; Aubé, J. J. Am. Chem. Soc. 2010, 132, 2078.Szostak, M.; Yao, L.; Aubé, J. J. Am. Chem. Soc. 2010, 132, 2078.
30. [30]
  Szostak, M.; Yao, L.; Day, V. W.; Powell, D. R.; Aubé, J. J. Am. Chem. Soc. 2010, 132, 8836.Szostak, M.; Yao, L.; Day, V. W.; Powell, D. R.; Aubé, J. J. Am. Chem. Soc. 2010, 132, 8836.
31. [31]
  Kozak, J. A.; Dake, G. R. Angew. Chem., Int. Ed. 2008, 47, 4221.Kozak, J. A.; Dake, G. R. Angew. Chem., Int. Ed. 2008, 47, 4221.
32. [32]
  Meng, G.; Szostak, M. Org. Biomol. Chem. 2016, 14, 5690.Meng, G.; Szostak, M. Org. Biomol. Chem. 2016, 14, 5690.
33. [33]
  Shi, S.; Meng, G.; Szostak, M. Angew. Chem. Int. Ed. 2016, 55, 6959.Shi, S.; Meng, G.; Szostak, M. Angew. Chem. Int. Ed. 2016, 55, 6959.
34. [34]
  Shi, S.; Szostak, M. Chem. Eur. J. 2016, 22, 10420.Shi, S.; Szostak, M. Chem. Eur. J. 2016, 22, 10420.
35. [35]
  Meng, G.; Szostak, M. Angew. Chem. Int. Ed. 2015, 54, 14518.Meng, G.; Szostak, M. Angew. Chem. Int. Ed. 2015, 54, 14518.

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沈阳化工大学材料科学与工程学院沈阳 110142

扭曲型酰胺——结构与功能

通讯作者: 史雷,Email:lshi@hit.edu.cn

English

The Twisted Amides: Structures and Functions

Corresponding author: Lei Shi, lshi@hit.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

扭曲型酰胺——结构与功能

通讯作者: 史雷,Email:lshi@hit.edu.cn

English

The Twisted Amides: Structures and Functions

Corresponding author: Lei Shi, lshi@hit.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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