SIOC English
有机化学
高级检索

有机化学 >

0 4046

DOI: https://doi.org/10.6023/cjoc202604046

空间受阻离子对催化缩醛及缩酮高效脱保护反应

  • 杨超 ,
  • 李若琪 ,
  • 张羽 ,
  • 邹明 ,
  • 陈朋 ,
  • 贾振华
展开
  • a河南工业大学前沿交叉科学与技术学院,郑州 450001;
    b复旦大学化学系,上海 200433

收稿日期: 2026-04-28

  修回日期: 2026-05-21

  网络出版日期: 2026-07-06

基金资助

国家自然科学青年基金(No.22401080)和河南工业大学高层次人才科研启动基金(No.2023BS006)等资助项目.

收起

Frustrated Ion-Pair Catalyzed Efficient Deprotection of Acetals and Ketals

  • Chao Yang ,
  • Ruoqi Li ,
  • Yu Zhang ,
  • Ming Zou ,
  • Peng Chen ,
  • Zhenhua Jia
Expand
  • aCollege of Advanced Interdisciplinary Science and Technology, Henan University of Technology, Zhengzhou, 450001;
    bDepartment of Chemistry, Fudan University, Shanghai, 200433

Received date: 2026-04-28

  Revised date: 2026-05-21

  Online published: 2026-07-06

Supported by

National Natural Science Foundation of China (No.22401080) and the Start-up Grant of Henan University of Technology (No.2023BS006).

Fold

摘要

缩醛和缩酮结构是羰基官能团的重要保护基之一,在有机合成化学中应用广泛。本文报道了空间受阻三芳基碳正离子离子对催化缩醛与缩酮的高效脱保护反应。在温和且无金属的反应条件下,脱保护反应时间仅需20分钟即可完成,而且该反应具有优异的官能团耐受性,以高产率（最高达98%）得到各类羰基化合物,底物范围涵盖各种类型的醛、酮、以及复杂天然产物分子。此外,该脱保护策略也成功应用于克级规模制备,反应操作简单,具有较强的实用性。

关键词： 无金属催化; 空间受阻离子对; 缩醛缩酮脱保护

本文引用格式

杨超 , 李若琪 , 张羽 , 邹明 , 陈朋 , 贾振华 . 空间受阻离子对催化缩醛及缩酮高效脱保护反应[J]. 有机化学, 0 : 4046 . DOI: 10.6023/cjoc202604046

Abstract

Acetals and ketals are among the most important protecting groups for carbonyl groups and are widely used in synthetic chemistry. In this work, we presented an efficient deprotection reaction for cyclic acetals and ketals catalyzed by triaryl carbenium ion-pair. Under mild and metal-free conditions within only 20 minutes, a wide range of carbonyl products were obtained in high yields (up to 98%) with excellent functional group tolerance, including aldehydes, ketones and natural products. Moreover, this deprotection process was practical for gram-scale synthesis, featuring simple operation and practical application.

Key words： Metal-free catalysis; Frustrated ion-pair; Deprotection of acetals and ketals

参考文献

[1] (a) Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 3rd ed.; John Wiley and Sons, Inc: New York, 1999.
(b) Hanson, J. R. Protecting Groups in Organic Synthesis, 1st ed.; Blackwell Science, Inc: Malden, MA, 1999.
(c) Kocienski, P. J. Protecting Groups, 1st ed.; Georg Thieme Verlag: Stuttgart, 1994.
(d) Wuts, P. G. M. Greene’s Protective Groups in Organic Synthesis, 5th edn, John Wiley & Sons Inc, 2014, pp. 554-685.
[2] (a) Torii, S.; Inokuchi, T.; Takagishi, S.; Horike, H.; Kuroda, H.; Uneyama, K. Bull. Chem. Soc. Jpn. 1987, 60, 2173-2188.
(b) Masui, M.; Kawaguchi, T.; Ozaki, S.J. Chem. Soc., Chem. Commun. 1985, 1484-1485.
(c) Martre A.-M.; Mousset G.; Rhlid R. B.; Veschambre H. Tetrahedron Lett.1990, 31, 2599-2602.
(d) Noji M.; Ishimaru S.; Obata H.; Kumaki A.; Seki T.; Hayashi, S. Takanami, T. Tetrahedron Lett.2022, 104, 154026.
[3] Gregg B. T.; Golden K. C.; Quinn, J. F. J. Org. Chem.2007, 72, 5890-5893.
[4] Olson M. E.; Carolan J. P.; Chiodo M. V.; Lazzara P. R.; Mohan, R. S. Tetrahedron Lett.2010, 51, 3969-3971.
[5] Fujioka H.; Sawama Y.; Murata N.; Okitsu T.; Kubo O.; Matsuda S.; Kita, Y. J. Am. Chem. Soc.2004, 126, 11800-11801.
[6] Fujioka H.; Okitsu T.; Sawama Y.; Murata N.; Li R.; Kita, Y. J. Am. Chem. Soc.2006, 128, 5930-5938.
[7] Yuan C.; Yang L.; Yue G.; Yu T.; Zhong W.; Liu B. Tetrahedron Lett.2012, 53, 6972-6976.
[8] Abe Y.; Yamada T.; Yamamoto T.; Esaka Y.; Ikawa T.; Sajiki H. Green Chem.2025, 27, 5464-5470.
[9] Li L.; He Z.; Zhang Z.; Jia Z.; Loh, T.-P. Chin. J. Org. Chem.2024, 44, 421-437 (in Chinese).
(李路瑶,贺忠文,张振国,贾振华,罗德平,有机化学,2024,44,421-437.)
[10] Zhang Z.; Liu X.; Ji L.; Zhang T.; Jia Z.; Loh T.-P.ACS Catal. 2022, 12, 2052-2057.
[11] Zhang Z.; Lv Y.; Ong W. Q. R.; Zhao X.; Jia Z.; Loh, T.-P. Angew. Chem. Int. Ed.2024, 63, e202408509.
[12] Zhu Y.; Yang C.; Lin Q.; Li J.; Loh T.-P.; Chen P.; Jia Z.Org. Lett. 2025, 27, 2110-2115.
[13] Wang L.; Mondal B.; Li B.; Zhang Z.; Loh T.-P.; Chen P.; Jia Z. ACS Catal.2025, 15, 19777-19785.
[14] Mondal B.; Wang L.; Wang S.; Loh T.-P. JACS Au.2026, 6, 357-366.
[15] Chen P.; Zou M.; Zhang Y.; Li N.; Li R.; Liang L.; Zhang Z.; Loh T.-P.; Jia Z. Green Chem.2026, 28, 4029-4035.
[16] (a) Totherow W. D.; Gleicher, G. J. J. Am. Chem. Soc.1969, 91, 7150-7154.
(b) Hansch C.; Leo A.; Taft, R. W. A Chem. Rev.1991, 91, 165-195.
[17] Marcantoni E.; Nobili F.; Bartoli G.; Bosco M.; Sambri, L. J. Org. Chem.1997, 62, 4183-4184.
[18] Furuta K.; Nagata T.; Yamamoto H. Tetrahedron Lett.1988, 29, 2215-2218.
[19] Tanemura K.; Suzuki T. Chem. Lett.2015, 44, 797-799.
[20] To T. A.; Nguyen, T. V. Angew. Chem. Int. Ed.2024, 63, e202317003.
[21] Barlow J. W.; McHugh A. P.; Woods O.; Walsh, J. J. Eur. J. Med. Chem.2011, 46, 1545-1554.
[22] Ma N.-N.; Hu X.-B.; Wu Y.-S.; Zheng Y.-W.; Ma M.; Chu X.-Q.; Xu H.; Luo H.; Shen Z.-L. Org. Lett.2023, 25, 1771-1775.
[23] Yan Y.; Sun S.; Cheng, J. J. Org. Chem.2017, 82, 12888-12891.
[24] Su M.; Huang X.; Lei C.; Jin J. Org. Lett.2022, 24, 354-358.
[25] Furuta K.; Nagata T.; Yamamoto H. Tetrahedron Lett.1988, 29, 2215-2218.
[26] Abe Y.; Yamada T.; Yamamoto T.; Esaka Y.; Ikawa T.; Sajiki H. Green Chem.2025, 27, 5464.
[27] Yi H.; Niu L.; Wang S.; Liu T.; Singh A. K.; Lei A. Org. Lett.2017, 19, 122-125.
[28] Jiang F.; Chen Y.; Zhang Q.; Wang W.Synlett 2024, 35, 2138-2142.
[29] Ma N.-N.; Hu X.-B.; Wu Y.-S.; Zheng Y.-W.; Ma M.; Chu X.-Q.; Xu H.; Luo H.; Shen Z.-L. Org. Lett.2023, 25, 1771-1775.
[30] Kim H.; Goseki R.; Homma C.; Ishizone T. Macromolecules2023, 56, 8796-8805.
[31] Yang T.; Liu Q.; Cheng Y.; Cai W.; Ma Y.; Yang L.; Wu Q.; Orband-Miller L. A.; Zhou L.; Xiang Z.; Huxdorf M.; Zhang W.; Zhang J.; Xiang J.-N.; Leung S.; Qiu Y.; Zhong Z.; Elliott J. D.; Lin X.; Wang, Y. ACS Med. Chem. Lett.2014, 5, 65-68.
[32] D’Hollander A. C. A.; Westwood N. J. Tetrahedron2018, 74, 224-239.
[33] Hergert T.; Varga B.; Thurner A.; Faigl F.; Mátravölgyi B.Tetrahedron 2018, 74, 2002-2008.
[34] Kang S.-H.; Lee D.; Kim H.; Choi W.; Oh J.; Oh J. H.; Yang, C. ACS Appl. Mater. Interfaces2021, 13, 52840-52849.
[35] Lindroth R.; Ondrejková A.; Wallentin C.-J. Org. Lett.2022, 24, 1662-1667.
[36] Katritzky A. R.; Odens H. H.; Voronkov, M. V. J. Org. Chem.2000, 65, 1886-1888.
[37] McKiernan G. J.; Hartley, R. C. Org. Lett.2003, 5, 4389-4392.
Options
文章导航

/

〈 〉