铜催化氟代丙烯酸与氧杂吖丙啶的脱羧交叉偶联反应

doi:10.6023/cjoc202208010

摘要/Abstract

报道了铜催化氟代丙烯酸与N-甲苯磺酰氧杂吖丙啶的脱羧偶联反应. 一系列含多种官能团的氟代丙烯酸均是兼容的反应底物. 一级、二级以及三级烷基取代的吖丙啶杂环都可以顺利地参与反应, 以中等以上的收率给出期望的单氟烯烃. 该脱羧反应展现出良好的官能团兼容性及卓越的立体选择性, 为在医药科学和材料科学上有着重要应用价值的单氟烯烃提供了一种新颖、实用的合成策略. 除了α-氟代肉桂酸, β-氟代肉桂酸也可以作为反应底物. 该方法可为多种取代类型的单氟烯烃提供合成途径, 该反应也为活性分子的后期修饰提供了策略.

关键词: 氟代丙烯酸, 吖丙啶, 铜催化, 单氟烯烃, 脱羧

A protocol for the copper-catalyzed decarboxylative cross-coupling of α‑fluoroacrylic acids with N-tosyl oxaziridines was reported. A series of substituted α-fluoroacrylic acids, and primary, secondary and tertiary substituted oxaziridines were suitable reaction substrates. The decarboxylation reaction exhibited good functional group compatibility and excellent Z-stereoselectivity. This method provides a novel and practical strategy for the construction of monofluoroalkenes, which are key functional groups in the pharmaceutical and material sciences. In addition to α-fluoroacrylic acids, β- fluoroacrylic acid could also participate in the reaction smoothly, which provides a protocol to access various substituted monofluoroalkenes. This methodology also provides a platform for the modification of complex biologically active molecules.

Key words: fluoroacrylic acids, oxaziridines, copper-catalyzed, monofluoroalkene, decarboxylative

引用此文

陆晓雨, 孙晓梅, 钮亚琴, 王俊超, 殷文婧, 高梦婷, 刘孜, 韦正桓, 陶庭骅. 铜催化氟代丙烯酸与氧杂吖丙啶的脱羧交叉偶联反应[J]. 有机化学, 2023, 43(6): 2110-2119.

Xiaoyu Lu, Xiaomei Sun, Yaqing Niu, Junchao Wang, Wenjing Yin, Mengting Gao, Zi Liu, Zhenghuan Wei, Tinghua Tao. Copper-Catalyzed Decarboxylative Cross-Coupling of α‑Fluoroacrylic Acids with N-Tosyl Oxaziridines[J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2110-2119.

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参考文献 19

[1]	(a) Hagmann, W. K. J. Med. Chem. 2008, 51, 4359. doi: 10.1021/jm800219f
	(b) Wang, J.; SánchezRoselló, M.; Aceña, J. L.; del Pozo, C.; Sorochinsky, A. E.; Fustero, S.; Soloshonok, V. A.; Liu, H. Chem. Rev. 2014, 114, 2432. doi: 10.1021/cr4002879
	(c) Liu, Q.; Ni, C.; Hu, J. Natl. Sci. Rev. 2017, 4, 303. doi: 10.1093/nsr/nwx058
	(d) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320. doi: 10.1039/B610213C
	(d) Liao, F.; Yu, J; Zhou, J. Chin. J. Org. Chem. 2017, 37, 2175. (in Chinese) doi: 10.6023/cjoc201705001
	(廖富民, 余金生, 周剑, 有机化学, 2017, 37, 2175.) doi: 10.6023/cjoc201705001
	(e) He, S.; Pi, J.; Li, Y.; Lu, X.; Fu, Y. Acta Chim. Sinica. 2018, 76, 956. (in Chinese) doi: 10.6023/A18080333
	(何世江, 皮静静, 李炎, 陆熹, 傅尧, 化学学报, 2018, 76, 956.) doi: 10.6023/A18080333
[2]	(a) O’Hagan, D.; Deng, H. Chem. Rev. 2015, 115, 634. doi: 10.1021/cr500209t
	(b) Shi, Y.; Xiao, T.; Xia, D.; Yang, W. Chin. J. Org. Chem. 2022, 42, 2715. (in Chinese) doi: 10.6023/cjoc202203041
	(石云, 肖婷, 夏冬, 杨文超, 有机化学, 2022, 42, 2715.) doi: 10.6023/cjoc202203041
	(c) Chen, D.; Jiang, J.; Wan, J.-P. Chin. J. Chem. 2022, 40, 2582. doi: 10.1002/cjoc.v40.21
[3]	(a) Kirsch, P. Modern Fluoroorganic Chemistry: Synthesis Reactivity Applications, Wiley-VCH, Weinheim, Germany, 2007.
	(b) Müller, K.; Faeh, C.; Diederich, F. Science 2007, 317, 1881. doi: 10.1126/science.1131943
	(c) Liang, T.; Neumann, C. N.; Ritter, T. Angew. Chem., Int. Ed. 2013, 52, 8214. doi: 10.1002/anie.v52.32
[4]	(a) Lin, G.-Q.; You, Q.-D.; Cheng, J.-F. Chiral Drugs: Chemistry and Biological Action, John Wiley & Sons, Inc., Hoboken, 2011.
	(b) Oishi, S.; Kamitani, H.; Kodera, Y.; Watanabe, K.; Kobayashi, K.; Narumi, T.; Tomita, K.; Ohno, H.; Naito, T.; Kodama, E.; Matsuoka, M.; Fujii, N. Org. Biomol. Chem. 2009, 7, 2872. doi: 10.1039/b907983a
	(c) Meanwell, N. A. J. Med. Chem. 2018, 61, 5822. doi: 10.1021/acs.jmedchem.7b01788
[5]	(a) Reddy, V. P. Organofluorine Compounds in Biology and Medicine, Elsevier, Amsterdam, 2015.
	(b) Kirsch, P. Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications, WileyVCH, Weinheim, 2013.
	(c) Berger, R.; Resnati, G.; Metrangolo, P.; Weber, E.; Hulliger, J. Chem. Soc. Rev. 2011, 40, 3496 doi: 10.1039/c0cs00221f
[6]	(a) Drouin, M.; Paquin, J.-F. Beilstein. J. Org. Chem. 2017, 13, 2637. doi: 10.3762/bjoc.13.262 pmid: 21399789
	(b) Landelle, G.; Bergeron, M.; Turcotte-Savard, M.-O.; Paquin, J.-F. Chem. Soc. Rev. 2011, 40, 2867. doi: 10.1039/c0cs00201a pmid: 21399789
	(c) Drouin, M.; Hamel, J.-D.; Paquin, J.-F. Synthesis 2018, 50, 881. doi: 10.1055/s-0036-1591867 pmid: 21399789
[7]	(a) Xu, J.; Ahmed, E.-A.; Xiao, B.; Lu, Q.-Q.; Wang, Y.-L.; Yu, C.-G.; Fu, Y. Angew. Chem., Int. Ed. 2015, 54, 8231. doi: 10.1002/anie.201502308
	(b) Jiang, Z.-T.; Huang, J.; Zeng, Y.; Hu, F.; Xia, Y. Angew. Chem., nt. Ed. 2021, 60, 10626.
[8]	(a) Wang, C.; Liu, Y.-C.; Xu, M.-Y.; Xiao, B. Org. Lett. 2021, 23, 4593. doi: 10.1021/acs.orglett.1c01289
	(b) Dutheuil, G.; Paturel, C.; Lei, X.; Couve-Bonnaire, S.; Pannecoucke, X. J. Org. Chem. 2006, 71, 4316. doi: 10.1021/jo0604787
	(c) Andrei, D.; Wnuk, S. F. J. Org. Chem. 2006, 71, 405. doi: 10.1021/jo051980e
	(d) Schneider, C.; Masi, D.; Couve-Bonnaire, S.; Pannecoucke, X.; Hoarau, C. Angew. Chem.,Int. Ed. 2013, 52, 3246. doi: 10.1002/anie.201209446
[9]	(a) Koley, S.; Altman, R. A. Isr. J. Chem. 2020, 60, 313. doi: 10.1002/ijch.v60.3-4
	(b) Ma, T.; Chen, Y.; Li, Y.; Ping, Y.; Kong, W. ACS Catal. 2019, 9, 9127. doi: 10.1021/acscatal.9b03172
	(c) Li, J.; Rao, W.; Wang, S.-Y.; Ji, S.-J. J. Org. Chem. 2019, 84, 11542. doi: 10.1021/acs.joc.9b01387
	(d) Yang, L.; Ji, W.-W.; Lin, E.; Li, J.-L.; Fan, W.-X.; Li, Q.; Wang, H. Org. Lett. 2018, 20, 1924. doi: 10.1021/acs.orglett.8b00471
[10]	(a) Tian, P.; Feng, C.; Loh, T.-P. Nat. Commun. 2015, 6, 7472. doi: 10.1038/ncomms8472
	(b) Kong, L.; Zhou, X.; Li, X. Org. Lett. 2016, 18, 6320. doi: 10.1021/acs.orglett.6b03203
	(c) Zell, D.; Dhawa, U.; Müller, V.; Bursch, M.; Grimme, S.; Ackermann, L. ACS Catal. 2017, 7, 4209. doi: 10.1021/acscatal.7b01208
	(d) Fuchibe, K.; Mayumi, Y.; Zhao, N.; Watanabe, S.; Yokota, M.; Ichikawa, J. Angew. Chem., Int. Ed. 2013, 52, 7825. doi: 10.1002/anie.v52.30
[11]	(a) Thornbury, R. T.; Toste, F. D. Angew. Chem., Int. Ed. 2016, 55, 11629. doi: 10.1002/anie.201605651 pmid: 26077810
	(b) Xiong, Y.; Huang, T.; Ji, X.; Wu, J.; Cao, S. Org. Biomol. Chem. 2015, 13, 7389. doi: 10.1039/c5ob01016k pmid: 26077810
[12]	(a) Lu, X.; Wang, Y.; Zhang, B.; Pi, J.-J.; Wang, X.-X.; Gong, T.-J.; Xiao, B.; Fu, Y. J. Am. Chem. Soc. 2017, 139, 12632. pmid: 30774912
	(b) Du, H.-W.; Sun, J.; Gao, Q.-S.; Wang, J.-Y.; Wang, H.; Xu, Z.; Zhou, M.-D. Org. Lett. 2020, 22, 1542. doi: 10.1021/acs.orglett.0c00134 pmid: 30774912
	(c) Dai, W.; Shi, H.; Zhao, X.; Cao, S. Org. Lett. 2016, 18, 4284. doi: 10.1021/acs.orglett.6b02026 pmid: 30774912
	(d) Zhou, L.; Zhu, C.; Bi, P.; Feng, C. Chem. Sci. 2019, 10, 1144. doi: 10.1039/c8sc04162h pmid: 30774912
	(e) Xie, J.; Yu, J.; Rudolph, M.; Rominger, F.; Hashmi, A. S. K. Angew. Chem., Int. Ed. 2016, 55, 9416. doi: 10.1002/anie.v55.32 pmid: 30774912
	(f) Yu, L.; Tang, M.-L.; Si, C.-M.; Meng, Z.; Liang, Y.; Han, J.; Sun, X. Org. Lett. 2018, 20, 4579. doi: 10.1021/acs.orglett.8b01866 pmid: 30774912
	(g) Yang, H.; Tian, C.; Qiu, D.; Tian, H.; An, G.; Li, G. Org. Chem. Front. 2019, 6, 2365. doi: 10.1039/c9qo00495e pmid: 30774912
	(h) Li, J.; Lefebvre, Q.; Yang, H.; Zhao, Y.; Fu, H. Chem. Commun. 2017, 53, 10299. doi: 10.1039/C7CC05758J pmid: 30774912
[13]	Lu, X.-Y.; Gao, A.; Ge, M.-Y.; Xia, Z.-J.; Liu, Q.-L.; Tao, T.-H.; Sun, X.-M. J. Org. Chem. 2022, 87, 4654. doi: 10.1021/acs.joc.1c03088
[14]	Lu, X.-Y.; Ge, M.-Y.; Tao, T.-H.; Sun, X.-M.; Gao, M.-T.; Bao, S.-T.; Liu, Q.-L.; Xia, Z.-J.; Xia, J. Org. Chem. Front. 2022, 9, 831. doi: 10.1039/D1QO01567B
[15]	Lu, X.-Y.; Chen, X.-K.; Gao, M.-T.; Sun, X.-M.; Jiang, R.-C.; Wang, J.-C.; Yu, L.-J.; Ge, M.-Y.; Wei, Z.-H.; Liu, Z. Org. Chem. Front. 2022, 9, 4712. doi: 10.1039/D2QO00977C
[16]	Chen, Y.; Du, J.; Zuo, Z. Chem 2020, 6, 266. doi: 10.1016/j.chempr.2019.11.009
[17]	(a) Xiao, T.; Zhou, L.; Huang, H.; Anand, D. Synthesis 2020, 52, 1585. doi: 10.1055/s-0039-1690844
	(b) Yu, X.-Y.; Zhao, Q.-Q.; Chen, J.; Xiao, W.-J.; Chen, J.-R. Acc. Chem. Res. 2020, 53, 1066. doi: 10.1021/acs.accounts.0c00090
	(c) Xiao, F.; Guo, Y.; Zeng, Y. F. Adv. Synth. Catal. 2021, 363, 120. doi: 10.1002/adsc.v363.1
	(d) Sivaguru, P.; Wang, Z.; Zanoni, G.; Bi, X. Chem. Soc. Rev. 2019, 48, 2615. doi: 10.1039/C8CS00386F
	(e) Xiao, W.; Wu, J. Chin. Chem. Lett. 2020, 31, 3083. doi: 10.1016/j.cclet.2020.07.035
	(f) Yu, X.-Y.; Chen, J.-R.; Xiao, W.-J. Chem. Rev. 2021, 121, 506. doi: 10.1021/acs.chemrev.0c00030
	(g) Lu, X.-Y.; Liu, C.-C.; Jiang, R.-C.; Yan, L.-Y.; liu, Q.-L.; Wang, Q.-Q.; Li, J.-M. Chem. Commun. 2020, 56, 14191. doi: 10.1039/D0CC06517J
	(h) Lu, X.-Y.; Xia, Z.-J.; Gao, A.; Liu, Q.-L.; Jiang, R.-C.; Liu, C.-C. J. Org. Chem. 2021, 86, 8829. doi: 10.1021/acs.joc.1c00726
[18]	(a) Nguyen, B.-N.; Cao, H.-T. Eur. J. Org. Chem. 2019, 20196, 5912.
	(b) Matsumoto, A.; Nguyen, B.-N.; Honda, T.; Sakamoto, R.; Huang, X.; Sakaki, S.; Maruoka, K. Chem. Asian J. 2021, 16, 282. doi: 10.1002/asia.v16.4
[19]	(a) Chen, L.; Zhang, L.; Yan, G.; Huang, D. Asian J. Org. Chem. 2020, 9, 842. doi: 10.1002/ajoc.v9.6
	(b) Lu, X.-Y.; Li, J.-S.; Wang, S.-Q.; Zhu, Y.-J.; Li, Y.-M.; Yan, L.-Y.; Li, J.-M.; Wang, J.-Y.; Zhou, H.-P.; Ge, X.-T. Chem. Commun. 2019, 55, 11123. doi: 10.1039/C9CC04795F

Entry^a	Catalyst	Ligand	Solvent	Yield/% (Z:E>30:1)
1	CuI	L1	DCE	37
2	CuBr	L1	DCE	26
3	CuCl	L1	DCE	25
4	CuTc	L1	DCE	55
5	Cu₂O	L1	DCE	62
6	CuOTf^.Ph	L1	DCE	40
7	Cu(CH₃CN)₄PF₆	L1	DCE	78
8	Fe(OAc)₂	L1	DCE	35
9	Cu(OTf)₂	L1	DCE	42
10	Cu(acac)₂	L1	DCE	72
11	CuO	L1	DCE	28
12	CuBr₂	L1	DCE	29
13	Cu(OAc)₂	L1	DCE	31
14	Cu(CH₃CN)₄PF₆	L2	DCE	37
15	Cu(CH₃CN)₄PF₆	L3	DCE	22
16	Cu(CH₃CN)₄PF₆	L4	DCE	18
17	Cu(CH₃CN)₄PF₆	L1	PhF	45
18	Cu(CH₃CN)₄PF₆	L1	PhCl	56
19	Cu(CH₃CN)₄PF₆	L1	PhH	43
20	Cu(CH₃CN)₄PF₆	L1	PhH/DCE (V:V=1:1)	38
21	Cu(CH₃CN)₄PF₆	L1	DCE	69
22	Cu(CH₃CN)₄PF₆	L1	DCE	65
23	—	L1	DCE	Trace

Entry^a	Catalyst	Ligand	Solvent	Yield/% (Z:E>30:1)
1	CuI	L1	DCE	37
2	CuBr	L1	DCE	26
3	CuCl	L1	DCE	25
4	CuTc	L1	DCE	55
5	Cu₂O	L1	DCE	62
6	CuOTf^.Ph	L1	DCE	40
7	Cu(CH₃CN)₄PF₆	L1	DCE	78
8	Fe(OAc)₂	L1	DCE	35
9	Cu(OTf)₂	L1	DCE	42
10	Cu(acac)₂	L1	DCE	72
11	CuO	L1	DCE	28
12	CuBr₂	L1	DCE	29
13	Cu(OAc)₂	L1	DCE	31
14	Cu(CH₃CN)₄PF₆	L2	DCE	37
15	Cu(CH₃CN)₄PF₆	L3	DCE	22
16	Cu(CH₃CN)₄PF₆	L4	DCE	18
17	Cu(CH₃CN)₄PF₆	L1	PhF	45
18	Cu(CH₃CN)₄PF₆	L1	PhCl	56
19	Cu(CH₃CN)₄PF₆	L1	PhH	43
20	Cu(CH₃CN)₄PF₆	L1	PhH/DCE (V:V=1:1)	38
21	Cu(CH₃CN)₄PF₆	L1	DCE	69
22	Cu(CH₃CN)₄PF₆	L1	DCE	65
23	—	L1	DCE	Trace