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2022 , Vol. 42 >Issue 7: 2098 - 2105

DOI: https://doi.org/10.6023/cjoc202203020

研究论文

钯催化的氯二氟乙基高价碘试剂对于乙酰苯胺C—H键的氯二氟乙基化反应研究

  • 曹成瑶 ,
  • 牛亚茹 ,
  • 蒋昀辰 ,
  • 曲红梅 ,
  • 陈超
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  • a清华大学化学系 生物有机磷化学与化学生物学教育部重点实验室 北京 100084
    b天津大学化工学院制药工程系 系统生物工程教育部重点实验室 天津 300350
    c南开大学 元素有机化学国家重点实验室 天津 300071

收稿日期: 2022-03-10

  修回日期: 2022-04-08

  网络出版日期: 2022-04-22

基金资助

国家重点研发项目(2016YFB0401400); 国家自然科学基金(22071129); 国家自然科学基金(21871158); 国家自然科学基金(21672120); 霍英东基金(151014)

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Pd-Catalyzed Chlorodifluoroethylation Reaction of C—H Bond of Acetanilides with Chlorodifluoroethyl Iodonium Reagents

  • Chengyao Kimmy Cao ,
  • Yaru Niu ,
  • Yunchen Jiang ,
  • Hongmei Qu ,
  • Chao Chen
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  • aKey Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084
    bKey Laboratory of Systems Bioengineering, Ministry of Education, Department of Pharmaceutical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350
    cState Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071
* E-mail:

Received date: 2022-03-10

  Revised date: 2022-04-08

  Online published: 2022-04-22

Supported by

National Key Research and Development Program of China(2016YFB0401400); National Natural Science Foundation of China(22071129); National Natural Science Foundation of China(21871158); the National Natural Science Foundation of China(21672120); Fok Ying Tong Education Foundation of China(151014)

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摘要

二氟乙基化合物在生物医药和材料领域有着广泛的应用, 合成二氟乙基的化合物有着重要意义, 在此报道了一种钯催化的乙酰苯胺邻位氯二氟乙基化的反应, 该反应利用氯二氟乙基高价碘试剂(CDFI)作为CH2CF2Cl的来源. 进一步研究发现, 有机碱1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU)加入到反应体系中, 可以通过消除反应制备乙酰苯胺邻位偕二氟乙烯基化产物.

关键词： C—H活化; 钯催化; 乙酰苯胺; 碘鎓盐; 氯二氟乙基化; 二氟乙烯基化

本文引用格式

曹成瑶 , 牛亚茹 , 蒋昀辰 , 曲红梅 , 陈超 . 钯催化的氯二氟乙基高价碘试剂对于乙酰苯胺C—H键的氯二氟乙基化反应研究[J]. 有机化学, 2022 , 42(7) : 2098 -2105 . DOI: 10.6023/cjoc202203020

Abstract

Difluoroethyl products have a wide range of applications in the fields of biomedicine and materials, and it is important to develop new method to synthesize difluoroethyl compounds. Herein, a palladium-catalyzed chlorodifluoroethylation was disclosed via ortho-C—H activation of acetanilide, using chlorodifluoroethyl(mesityl) hypervalent iodine reagent as the source of CH2CF2Cl. Moreover, adding organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to the above system, the difluorovinylated acetanilide products were obtained via an elimination reaction.

Key words： C—H activation; palladium catalyzed; acetanilide; iodonium salts; chlorodifluoroethylation; difluorovinylation

参考文献

[1]
(a) Caron, S. Org. Process Res. Dev. 2020, 24, 470.
[1]
(b) Berger, R.; Resnati, G.; Hulliger, J. Chem. Soc. Rev. 2011, 40, 3496.
[2]
(a) Magueur, G.; Bonnet-Delpon, D.; Be?gue?, J. P. J. Fluorine Chem. 2006, 127, 637.
[2]
(b) Meanwell, N. A. J. Med. Chem. 2011, 54, 2529.
[2]
(c) Torre de La, B. G.; Albericio, F. Molecules 2020, 25, 745.
[3]
Magueur, G.; Bonnet-Delpon, D.; Bégué, J. P. J. Fluorine Chem. 2006, 127, 637.
[4]
Karst, N. A.; Islam, T. F.; Linhardt, R. J. Org. Lett. 2003, 5, 4839.
[5]
Wang, W.; Liu, G.; Jiao, N. CCS Chem. 2020, 2, 566.
[6]
(a) Deng, X. Y.; Lin, J. H.; Xiao, J. C. Org. Lett. 2016, 18, 4384.
[6]
(b) Feng, Z.; Min, Q. Q.; Zhang, X. Nat. Chem. 2017, 9, 918.
[6]
(c) Feng, Z.; Min, Q. Q.; Zhang, X. Angew. Chem., Int. Ed. 2014, 53, 1669.
[6]
(d) Feng, Z.; Xiao, Y.L.; Zhang, X. Acc. Chem. Res. 2018, 51, 2264.
[6]
(e) Li, L.; Wang, F.; Hu, J. Angew. Chem., Int. Ed. 2020, 52, 12390.
[6]
(f) Salomon, P.; Zard, S. Z. Org. Lett. 2014, 16, 2926.
[6]
(g) Wang, F.; Li, L.; Hu, J. Beilstein. J. Org. Chem. 2014, 10, 344.
[6]
(h) Wang, F.; Prakash, G. K.; Olah, G. A. Angew. Chem., Int. Ed. 2011, 50, 7153.
[6]
(i) Zhang, H.; Lan, Y.; Liu, G. S. ACS Catalysis 2018, 8, 2173.
[6]
(j) Zheng, J.; Hu., J.; Federsel, H. J. Chem. Commun. 2007, 5149.
[7]
(a) Zhang, X.; Cao, S. Tetrahedron Lett. 2017, 58, 375.
[7]
(b) Chelucci, G. Chem. Rev. 2012, 112, 1344.
[7]
(c) Prakash, G. K. S.; Hu, J. B.; Olah, G. A. J. Fluorine Chem. 2006, 127, 1361.
[7]
(d) Nowak, I.; Robins, M. J. Org. Lett. 2005, 7, 721.
[7]
(e) Zhao, Y.; Zhu, L.; Hu, J. Org. Lett. 2010, 12, 1444.
[8]
(a) Khake, S. M.; Chatani, N. Chem 2020, 6, 1056.
[8]
(b) He, J.; Shao, Q.; Yu, J. Q. Chem. Rev. 2017, 117, 8754.
[8]
(c) Rej, S.; Ano, Y.; Chatani, N. Chem. Rev. 2020, 120, 1788.
[8]
(d) Zhang, Q.; Shi, B. F. Chin. J. Chem. 2019, 37, 647.
[8]
(e) Gandeepan, P.; Warratz, S.; Ackermann, L. Chem. Rev. 2019, 119, 2192.
[9]
(a) Liu, L. Y.; Qiao, J. X.; Yu, J. Q. J. Am. Chem. Soc. 2019, 141, 14870.
[9]
(b) Font, M.; Quibell, J. M.; Larrosa, I. Chem. Commun. 2017, 53, 5584.
[9]
(c) Nishikata, T.; Huang, S.; Lipshutz, B. H. J. Am. Chem. Soc. 2010, 132, 4978.
[9]
(d) Nishikata, T.; Abela, A. R.; Lipshutz, B. H. Angew. Chem., Int. Ed. 2010, 49, 781.
[9]
(e) Jiang, Z.; Xu, L.; Fan, Q. RSC Adv. 2020, 3, 1025.
[9]
(f) Jiang, P.; Yu, R.; Wang, Q. Org. Lett. 2015, 17, 5918.
[10]
(a) Aihara, Y.; Chatani, N. J. Am. Chem. Soc. 2020, 135, 5308.
[10]
(b) Song, W.; Lackner, S.; Ackermann, L. Angew. Chem., Int. Ed. 2014, 53, 2477.
[10]
(c) Shabashov, D.; Daugulis, O. J. Am. Chem. Soc. 2010, 132, 3965.
[10]
(d) Zhang, S. Y.; Li, Q.; Chen, G. J. Am. Chem. Soc. 2020, 135, 2124.
[10]
(e) Zhang, S. Y.; Li, Q.; Chen, G. J. Am. Chem. Soc. 2020, 135, 12135.
[10]
(f) Zhang, H.; Chen, P.; Liu, G. Angew. Chem., Int. Ed. 2014, 53, 10174.
[10]
(g) Zhang, H.; Chen, P.; Liu, G. Angew. Chem., Int. Ed. 2014, 126, 10338.
[10]
(h) Fujiwara, Y.; Ishihara, Y.; Baran, P. S. Nature 2012, 492, 95.
[11]
(a) Yusubov, M. S.; Zhdankin, V. V. Curr. Org. Synth. 2012, 9, 247.
[11]
(b) Yoshimura, A.; Zhdankin, V. V. Chem. Rev. 2016, 116, 3328.
[11]
(c) Han, Y. C. Zhang, C. Tetrahedron Lett. 2018, 59, 3052.
[11]
(d) Bal, A.; Maiti, S.; Mal, P. Chem. Asian J. 2020, 15, 624.
[11]
(e) Takenaga, N.; Kumar, R.; Dohi, T. Front. Chem. 2020, 8, 599026.
[11]
(f) Shetgaonkar, S. E.; Singh, F. V. Front. Chem. 2020, 8, 705.
[11]
(g) Wang, Y.; Chen, C.; Peng, J. Angew. Chem., Int. Ed. 2013, 52, 5323.
[11]
(h) Dong, D. Q.; Hao, S. H.; Chen, C. Org. Biomol. Chem. 2014, 12, 4278.
[11]
(i) Chen, J.; Chen, C; Qu, H. Chem. Commun. 2015, 51, 1356.
[11]
(j) Peng, J.; Chen, C.; Xi, C. Chem. Sci. 2016, 7, 1383.
[11]
(k) Sheng, J.; Wang, Y.; Chen, C. Angew. Chem., Int. Ed. 2017, 56, 4824.
[11]
(l) Sheng, J.; Wu, C.; Chen, C. Org. Lett. 2018, 20, 4458.
[11]
(m) Lin, J.; Zhou, J.; Chen, C. Eur. J. Org. Chem. 2019, 34 ,5963.
[12]
(a) Yan, T.; Chen, C.; Wen, L. Chin. J. Org. Chem. 2021, 41, 3660. (in Chinese)
[12]
( 颜廷勋, 陈超, 文丽荣, 有机化学, 2021, 41, 3660.)
[12]
(b) Niu, Y.; Qu, H.; Chen, C. Chin. Chem. Lett. 2022, 31, 1541.
[13]
The synthesis of fluoro-containing compounds developed by our group: (a) Cai, S.; Chen, C.; Sun, Z.; Xi, C. Chem. Commun. 2013, 49, 4552.
[13]
(b) Cao, C. K.; Tretyakov, E.; Chen, C. Green Synth. Catal. 2021, 2, 62.
[14]
(a) Maraswami, M.; Pankajakshan, S.; Chen, G. Org. Lett. 2017, 19, 4223.
[14]
(b) Kovacs, S.; Stirling, A.; Novak, Z. Adv. Synth. Catal. 2017, 359, 527.
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