Citation: Zhang Heng, Mou Xueqing, Chen Gong, He Gang. Copper-catalyzed Intramolecular Aminoperfluoroalkylation Reaction of O-Homoallyl Benzimidates[J]. Acta Chimica Sinica, ;2019, 77(9): 884-888. doi: 10.6023/A19060220 shu

Copper-catalyzed Intramolecular Aminoperfluoroalkylation Reaction of O-Homoallyl Benzimidates

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071

Corresponding author: Chen Gong, gongchen@nankai.edu.cn He Gang, hegang@nankai.edu.cn
Received Date: 18 June 2019
Available Online: 13 September 2019
Fund Project: Project supported by the National Natural Science Foundation of China (21672105, 21702109, 21890722), Natural Science Foundation of Tianjin (17JCYBJC19700, 18JCZDJC32800), and the Fundamental Research Funds for the Central Universities (Nankai University (No. 63161122)). We dedicate this work to the 100^th anniversary of Nankai University

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Azaheterocycles have been broadly applied in the development of therapeutic agents, agrochemicals and functional material molecules. Azaheterocycles equipped with perfluoroalkyl group usually manifest superior physical and biological properties than their parent molecules, such as showing improved metabolic stability and high lipophilicity. The synthesis of perfluoroalkyl modified azaheterocycles has attracted considerable research interest in recent years. The strategy of intramolecular aminoperfluoroalkylation of alkenes, which functionalize C=C bond with an external perfluoroalkyl group and an internal amine nucleophile in one pot, provides a streamlined synthesis of perfluoroalkyl substituted azaheterocycles. This strategy has been applied by Liu, Sodeoka and other research groups in the synthesis of perfluoroalkyl substituted aziridines, pyrrolidines, lactams and pyrazolines featuring the use of pendent amine, amide, hydrazone or urea group as internal amine source. We have previously developed a copper(Ⅰ)-catalyzed intramolecular aminotrifluoromethylation reaction of O-homoallyl benzimidates with Togni reagent Ⅰ for the synthesis of trifluoromethyl containing chiral 1, 3-oxazines using a chiral BOX ligand. However, this method is limited to aminotrifluoromethylation reaction as other perfluoroalkyl substituted hypervalent iodine reagents are not easily accessible. Herein, we report our recent research results on the synthesis of perfluoroalkyl substituted 1, 3-oxazines using commercial available perfluoroalkyl iodides as perfluoroalkyl source. This intramolecular aminoperfluoroalkylation reaction proceeds selectively in the presence of Cu(OAc)₂ catalyst, 1, 10-phenanthroline ligand and AgOAc additive. A broad range of O-homoallyl benzimidates and perfluoroalkyl iodides are compatible with the reaction conditions, affording perfluoroalkyl substituted 1, 3-oxazines in moderate to good yields. The 1, 3-oxazine product can be prepared in gram scale and readily hydrolyzed under mild conditions to give perfluoroalkyl substituted 1, 3-amino alcohols. Preliminary mechanism studies revealed that this intramolecular aminoperfluoroalkylation reaction initiated with the addition of a perfluoroalkyl radical to the terminal alkene, and the subsequent functionalization with the benzimidate motif via intramolecular substitution generated 1, 3-oxazine products.
- O-homoallyl benzimidates,
- aminoperfluoroalkylation,
- perfluoroalkyl iodides,
- 1, 3-oxazines,
- copper catalysis
1. [1]
  Hu, J.; Ding, K. Acta Chim. Sinica 2018, 76, 905(in Chinese). doi: 10.3969/j.issn.0253-2409.2018.08.002
2. [2]
  (a) Smart, B. E. J. Flurorine Chem. 2001, 109, 3; (b) Hagmann, W. K. J. Med. Chem. 2008, 51, 4359; (c) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320; (d) Zhou, Y.; Wang, J.; Gu, Z.; Wang, S.; Zhu, W.; Acena, J. L.; Soloshonok, V. A.; Izawa, K.; Liu, H. Chem. Rev. 2016, 116, 422.
3. [3]
  (a) Vitaku, E.; Smith, D. T.; Njardarson, J. T. J. Med. Chem. 2014, 57, 10257; (b) Meyer, F. Chem. Commun. 2016, 52, 3077.
4. [4]
  Tian, Y.; Chen, S.; Gu, Q.-S.; Lin, J.-S.; Liu, X.-Y. Tetrahedron Lett. 2018, 59, 203. doi: 10.1016/j.tetlet.2017.12.034
5. [5]
  (a) Takamasa, F.; Yoshiko, S.; Hisao, U. Chem. Lett. 1987, 16, 521; (b) Kim, E.; Choi, S.; Kim, H.; Cho, E. J. Chem.-Eur. J. 2013, 19, 6209; (c) Matcha, K.; Antonchick, A. P. Angew. Chem., Int. Ed. 2014, 53, 11960; (d) Wei, Q.; Chen, J.-R.; Hu, X.-Q.; Yang, X.-C.; Lu, B.; Xiao, W.-J. Org. Lett. 2015, 17, 4464; (e) Jarrige, L.; Carboni, A.; Dagousset, G.; Levitre, G.; Magnier, E.; Masson, G. Org. Lett. 2016, 18, 2906.
6. [6]
  For copper catalyzed intramolecular aminoperfuoroalkylation, see: (a) Egami, H.; Kawamura, S.; Miyazaki, A.; Sodeoka, M. Angew. Chem., Int. Ed. 2013, 52, 7841; (b) Kawamura, S.; Egami, H.; Sodeoka, M. J. Am. Chem. Soc. 2015, 137, 4865; (c) Kawamura, S.; Dosei, K.; Valverde, E.; Ushida, K.; Sodeoka, M. J. Org. Chem. 2017, 82, 12539; (d) Lin, J.-S.; Liu, X.-G.; Zhu, X.-L.; Tan, B.; Liu, X.-Y. J. Org. Chem. 2014, 79, 7084; (e) Lin, J.-S.; Xiong, Y.-P.; Ma, C.-L.; Zhao, L.-J.; Tan, B.; Liu, X.-Y. Chem.-Eur. J. 2014, 20, 1332; (f) Li, X.-F.; Lin, J.-S.; Liu, X.-Y. Synthesis 2017, 49, 4213; (g) Shen, K.; Wang, Q. Org. Chem. Front. 2016, 3, 222; (h) Yu, L.-Z.; Wei, Y.; Shi, M. Chem. Commun. 2016, 52, 13163; (i) Zhang, H.-Y.; Huo, W.; Ge, C.; Zhao, J.; Zhang, Y. Synlett 2017, 28, 962; (j) Chang, B.; Su, Y.; Huang, D.; Wang, K.-H.; Zhang, W.; Shi, Y.; Zhang, X.; Hu, Y. J. Org. Chem. 2018, 83, 4365.
7. [7]
  For enantioselective aminotrifluoromethylation of alkene, see: (a) Lin, J.-S.; Dong, X.-Y.; Li, T.-T.; Jiang, N.-C.; Tan, B.; Liu, X.-Y. J. Am. Chem. Soc. 2016, 138, 9357; (b) Lin, J.-S.; Wang, F.-L.; Dong, X.-Y.; He, W.-W.; Yuan, Y.; Chen, S.; Liu, X.-Y. Nat. Commun. 2017, 8, 14841.
8. [8]
  For recent examples of using imidates as nucleophile, see: (a) Brindle, C. S.; Yeung, C. S.; Jacobsen, E. N. Chem. Sci. 2013, 4, 2100; (b) Zhu, R.; Yu, K.; Gu, Z. Org. Biomol. Chem. 2014, 12, 6653.
9. [9]
  Mou, X.-Q.; Chen, X.-Y.; Chen, G.; He, G. Chem. Commun. 2018, 54, 515. doi: 10.1039/C7CC08897C
10. [10]
  For selected examples of intramolecular C-H amination of imidates by other groups, see: (a) Wappes, E. A.; Nakafuku, K. M.; Nagib, D. A. J. Am. Chem. Soc. 2017, 139, 10204; (b) Stateman, L. M.; Wappes, E. A.; Nakafuku, K. M.; Edwards, K. M.; Nagib, D. A. Chem. Sci. 2019, 10, 2693; (c) Shaw, M.; Kumar, A. Org. Lett. 2019, 21, 3108.
11. [11]
  Mou, X.-Q.; Rong, F.-M.; Zhang, H.; Chen, G.; He, G. Org. Lett. 2019, 21, 4657. doi: 10.1021/acs.orglett.9b01552
12. [12]
  (a) Eisenberger, P.; Gischig, S.; Togni, A. Chem.-Eur. J. 2006, 12, 2579; (b) Matoušek, V.; Pietrasiak, E.; Schwenk, R.; Togni, A. J. Org. Chem. 2013, 78, 6763; (c) Charpentier, J.; Früh, N.; Togni, A. Chem. Rev. 2015, 115, 650.
13. [13]
14. [14]
15. [15]
  For selected examples of perfluoroalkylation of aromatic compounds with perfluoroalkyl iodides, see (a) Iqbal, N.; Choi, S.; Ko, E.; Cho, E. J. Tetrahedron Lett. 2012, 53, 2005; (b) Barata-Vallejo, S.; Flesia, M. M.; Lanta o, B.; Argüello, J. E.; Pe é ory, A. B.; Postigo, A. Eur. J. Org. Chem. 2013, 2013, 998; (c) Straathof, N. J. W.; Gemoets, H. P. L.; Wang, X.; Schouten, J. C.; Hessel, V.; No l, T. ChemSusChem 2014, 7, 1612; (d) Huang, Y.; Lei, Y.-Y.; Zhao, L.; Gu, J.; Yao, Q.; Wang, Z.; Li, X.-F.; Zhang, X.; He, C.-Y. Chem. Commun. 2018, 54, 13662; (e) Yerien, D. E.; Cooke, M. V.; García Vior, M. C.; Barata-Vallejo, S.; Postigo, A. Org. Biomol. Chem. 2019, 17, 3741.
16. [16]
  For selected examples of perfluoroalkylation of alkene with perfluoroalkyl iodides under visible light irradiation, see (a) Brace, N. O. J. Org. Chem. 1963, 28, 3093; (b) Habib, M. H.; Mallouk, T. E. J. Flurorine Chem. 1991, 53, 53; (c) Ogawa, A.; Imura, M.; Kamada, N.; Hirao, T. Tetrahedron Lett. 2001, 42, 2489; (d) Tsuchii, K.; Imura, M.; Kamada, N.; Hirao, T.; Ogawa, A. J. Org. Chem. 2004, 69, 6658; (e) Wallentin, C.-J.; Nguyen, J. D.; Finkbeiner, P.; Stephenson, C. R. J. J. Am. Chem. Soc. 2012, 134, 8875; (f) Mizuta, S.; Verhoog, S.; Engle, K. M.; Khotavivattana, T.; O'Duill, M.; Wheelhouse, K.; Rassias, G.; Médebielle, M.; Gouverneur, V. J. Am. Chem. Soc. 2013, 135, 2505; (g) Wang, Y.; Wang, J.; Li, G.-X.; He, G.; Chen, G. Org. Lett. 2017, 19, 1442; (h) Beniazza, R.; Remisse, L.; Jardel, D.; Lastécouères, D.; Vincent, J.-M. Chem. Commun. 2018, 54, 7451; (j) Rawner, T.; Lutsker, E.; Kaiser, C. A.; Reiser, O. ACS Catal. 2018, 8, 3950.
17. [17]
  For selected examples of transition metal catalyzed perfluoroalkylation of alkene with perfluoroalkyl iodides, see: (a) Gil-Rubio, J.; Guerrero-Leal, J.; Blaya, M.; Vicente, J.; Bautista, D.; Jones, P. G. Organometallics 2012, 31, 1287; (b) Blaya, M.; Bautista, D.; Gil-Rubio, J.; Vicente, J. Organometallics 2017, 36, 1245; (c) Zheng, J.; Chen, P.; Yuan, Y.; Cheng, J. J. Org. Chem. 2017, 82, 5790.
18. [18]
  For selected reviews on the synthesis and application of 1, 3-oxazines, see: (a) Schmidt, R. R. Synthesis 1972, 1972, 333; (b) Sato, M.; Sunami, S.; Kaneko, C. Heterocycles 1996, 42, 861.
19. [19]
  In the reaction of O-homoallyl benzimidates equipped with multi-substituted alkene and trichloroacetimidate analogue of 1, no desired product was detected, and most of the starting material remain unconsumed.
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