Electrochemical 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO)-Mediated α-Cyanation and Phosphonylation of Cyclic Amines with Metal-Free Conditions

doi:10.6023/cjoc202103049

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (8): 3223-3234.DOI: 10.6023/cjoc202103049 Previous Articles Next Articles

Special Issue: 有机电合成虚拟专辑

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无金属参与的电化学促进2,2,6,6-四甲基哌啶-氮-氧化物(TEMPO)介导的环胺α-氰化和膦酰化反应

高君青^a, 翁信军^b, 马聪^b, 徐学涛^a^,^*(), 方萍^b^,^*(), 梅天胜^b^,^*()

a 五邑大学生物科技与大健康学院广东江门 529020
b 中国科学院上海有机化学研究所金属有机化学国家重点实验室分子合成卓越中心上海 200032

收稿日期:2021-03-26 修回日期:2021-04-26 发布日期:2021-05-14
通讯作者: 徐学涛, 方萍, 梅天胜
作者简介:
† 共同第一作者
基金资助:
国家自然科学基金(21772222); 国家自然科学基金(21821002); 广东省教育厅基金(2017KSYS010); 广东省教育厅基金(2017KZDXM084); 广东省教育厅基金(2019KZDZX2003); 广东省教育厅基金(2019KZDXM035)

Electrochemical 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO)-Mediated α-Cyanation and Phosphonylation of Cyclic Amines with Metal-Free Conditions

Junqing Gao^a, Xinjun Weng^b, Cong Ma^b, Xuetao Xu^a(), Ping Fang^b(), Tiansheng Mei^b()

a School of Biotechnology and Health Science, Wuyi University, Jiangmen, Guangdong 529020
b Center for Excellence in Molecular Synthesis, State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2021-03-26 Revised:2021-04-26 Published:2021-05-14
Contact: Xuetao Xu, Ping Fang, Tiansheng Mei
About author:
† (These authors contributed equally to this work).
Supported by:
National Natural Science Foundation of China(21772222); National Natural Science Foundation of China(21821002); Department of Education of Guangdong Province(2017KSYS010); Department of Education of Guangdong Province(2017KZDXM084); Department of Education of Guangdong Province(2019KZDZX2003); Department of Education of Guangdong Province(2019KZDXM035)

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Abstract

Metal-free electrochemical oxidation cyanation and phosphonylation reactions had been developed, in which 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO) reduced the electrode potential of substrate and avoided over oxidation of some electron rich aromatic amines under electrochemical conditions. This protocol had good functional group compatibility, which made it to be a practical and efficient method to synthesize α-aminonitriles and α-amino phosphonates under mild conditions. Preliminary study indicated that the formation of the product was through the Shono oxidation of imine species.

Key words: electrochemistry, Shono oxidation, cyanation, phosphonylation

Cite this article

Junqing Gao, Xinjun Weng, Cong Ma, Xuetao Xu, Ping Fang, Tiansheng Mei. Electrochemical 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO)-Mediated α-Cyanation and Phosphonylation of Cyclic Amines with Metal-Free Conditions[J]. Chinese Journal of Organic Chemistry, 2021, 41(8): 3223-3234.

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Fig. & Tab. 8

References 27

[1]	(a) Weinstock, L. M.; Davis, P.; Handelsman, B.; Tull, R. J. J. Org. Chem. 1967, 32, 2823. doi: 10.1021/jo01284a040 pmid: 4745833
	(b) Matier, W. L.; Owens, D. A.; Comer, W. T.; Deitchman, D.; Ferguson, H. C. Seidehamel, R. J.; Young, J. R. J. Med. Chem. 1973, 16, 901. pmid: 4745833
	(c) Enders, D.; Shilvock, J. P. Chem. Soc. Rev. 2000, 29, 359. doi: 10.1039/a908290e pmid: 4745833
[2]	(a) Shono, T.; Matsumura, Y.; Uchida, K.; Tsubata, K.; Makino, A. J. Org. Chem. 1984, 49, 300. doi: 10.1021/jo00176a016 pmid: 25147957
	(b) Myers, E. L.; de Vries, J. G.; Aggarwal, V. K. Angew. Chem. Int. Ed. 2007, 46, 1893. doi: 10.1002/(ISSN)1521-3773 pmid: 25147957
	(c) Kabeshov, M. A.; Musio, B.; Murray, P. R.; Browne, D. L.; Ley, S. V. Org. Lett. 2014, 16, 4618. doi: 10.1021/ol502201d pmid: 25147957
[3]	(a) Moeller, K. D.; Wong, P. L. Bioorg. Med. Chem. Lett. 1992, 2, 739. doi: 10.1016/S0960-894X(00)80403-5
	(b) Frankowski, K. J.; Liu, R.; Milligan, G. L.; Moeller, K. D.; Aube, J. Angew. Chem. Int. Ed. 2015, 54, 10555. doi: 10.1002/anie.201504775
[4]	Myers, E. L.; de Vries, J. G.; Aggarwal, V. K. Angew. Chem. 2007, 119, 1925. doi: 10.1002/(ISSN)1521-3757
[5]	(a) Rappoport, Z. The Chemistry of the Cyano Group, Interscience Publishers, London, 1970.
	(b) Larock, R. C. Comprehensive Organic Transformations: A Guide to Functional Group Preparations, VCH, New York, 1989.
[6]	For selected examples on Fe-catalyzed, see:
	(a) Singhal, S.; Jain, S. L.; Sain, B. Adv. Synth. Catal. 2010, 352, 1338. doi: 10.1002/adsc.v352:8
	(b) Liu, P.; Liu, Y.; Wong, E. L-M.; Xiang, S.; Che, C.-M. Chem. Sci. 2011, 2, 2187. doi: 10.1039/c1sc00234a
	(c) Sun, C. L.; Li, B. J.; Shi, Z. J. Chem. Rev. 2011, 111, 1293. doi: 10.1021/cr100198w
	(d) Wagner, A.; Han, W.; Mayer, P.; Ofial, A. R. Adv. Synth. Catal. 2013, 355, 3058. doi: 10.1002/adsc.v355.14/15
	(e) Patil, M.; Kapdi, A. R.; Kumar, A. V. RSC Adv. 2015, 5, 54505. doi: 10.1039/C5RA10552H
	(f) Wagner, A.; Hampel, N.; Zipse, H.; Ofial, A. R. Org. Lett. 2015, 17, 4770. doi: 10.1021/acs.orglett.5b02319
	(g) Nauth, A. M.; Otto, N.; Opatz, T. Adv. Synth. Catal. 2015, 357, 3424. doi: 10.1002/adsc.201500698
	(h) Panwar, V.; Kumar, P.; Bansal, A.; Ray, S. S.; Jain, S. L. Appl. Catal., 2015, 498, 25. doi: 10.1016/j.apcata.2015.03.018
	(i) Zhang, L.; Gu, X.; Lu, P.; Wang, Y. Tetrahedron 2016, 72, 2359. doi: 10.1016/j.tet.2016.03.061
	(j) Huang, M.; Deng, Q.; Gao, Q.; Shi, J.; Zhang, X.; Xiong, Y. Asian J. Org. Chem. 2018, 7, 404. doi: 10.1002/ajoc.v7.2
[7]	For selected examples on Cu-catalyzed, see: pmid: 27934338
	(a) Li, Z.; Li, C.-J. Eur. J. Org. Chem., 2005, 2005, 3173. doi: 10.1002/(ISSN)1099-0690 pmid: 27934338
	(b) Han, W.; Ofial, A. R. Chem. Commun. 2009, 5024. pmid: 27934338
	(c) Ogibin, Y. N.; Elinson, M. N.; Nikishin, G. I. Russ. Chem. Rev. 2009, 78, 89. doi: 10.1070/RC2009v078n02ABEH003886 pmid: 27934338
	(d) Boess, E.; Schmitz, C.; Klussmann, M. J. Am. Chem. Soc. 2012, 134, 5317. doi: 10.1021/ja211697s pmid: 27934338
	(e) Zhang, G.; Ma, Y.; Cheng, G.; Liu, D.; Wang, R. Org. Lett. 2014, 16, 656. doi: 10.1021/ol500045p pmid: 27934338
	(f) Fandrick, D. R.; Hart, C. A.; Okafor, I. S.; Mercadante, M. A.; Sanyal, S.; Masters, J. T.; Sarvestani, M.; Fandrick, K. R.; Stockdill, J. L.; Grinberg, N.; Gonnella, N.; Lee, H.; Senanayake, C. H. Org. Lett. 2016, 18, 6192. pmid: 27934338
	(g) Liu, Y.; Wang, C.; Xue, D.; Xiao, M.; Li, C.; Xiao, J. Chem.- Eur. J. 2017, 23, 3051. doi: 10.1002/chem.201604749 pmid: 27934338
[8]	For selected examples on Ir-catalyzed, see: a Rueping, pmid: 30160970
	(a) Rueping, M.; Zhu, S.; Koenigs, R. M. Chem. Commun. 2011, 47, 12709. doi: 10.1039/c1cc15643h pmid: 30160970
	(b) Verma, D.; Verma, S.; Sinha, A. K.; Jain, S. L. ChemPlusChem 2013, 78, 860. doi: 10.1002/cplu.201300196 pmid: 30160970
	(c) Ide, T.; Shimizu, K.; Egami, H.; Hamashima, Y. Tetrahedron Lett. 2018, 59, 3258. doi: 10.1016/j.tetlet.2018.07.030 pmid: 30160970
	(d) Yilmaz, O.; Oderinde, M. S.; Emmert, M. H. J. Org. Chem. 2018, 83, 11089. doi: 10.1021/acs.joc.8b01700 pmid: 30160970
[9]	For selected examples on Ru-catalyzed, see:
	(a) Murahashi, S. I.; Komiya, N.; Terai, H.; Nakae, T. J. Am. Chem. Soc. 2003, 125, 15312. doi: 10.1021/ja0390303
	(b) North, M. Angew. Chem. Int. Ed. 2004, 43, 4126. doi: 10.1002/(ISSN)1521-3773
	(c) Murahashi, S.; Komiya, N.; Terai, H. Angew. Chem. Int. Ed. 2005, 44, 6931. doi: 10.1002/(ISSN)1521-3773
	(d) Murahashi, S. I.; Nakae, T.; Terai, H.; Komiya, N. J. Am. Chem. Soc. 2008, 130, 11005. doi: 10.1021/ja8017362
	(e) Verma, S.; Jain, S. L.; Sain, B. ChemCatChem 2011, 3, 1329. doi: 10.1002/cctc.201100111
	(f) Verma, S.; Jain, S. L.; Sain, B. Catal. Lett. 2011, 141, 882. doi: 10.1007/s10562-011-0582-6
	(g) Schümperli, M. T.; Hammond, C.; Hermans, I. ACS Catal. 2012, 2, 1108. doi: 10.1021/cs300212q
	(h) Panwar, V.; Ray, S. S.; Jain, S. L. Tetrahedron Lett. 2015, 56, 4184. doi: 10.1016/j.tetlet.2015.05.033
[10]	For selected examples on Ti-catalyzed, see:
	(a) Rueping, M.; Zoller, J.; Fabry, D. C.; Poscharny, K.; Koenigs, R. M.; Weirich, T. E.; Mayer, J. Chem.-Eur. J. 2012, 18, 3478. doi: 10.1002/chem.201103242
	(b) Kumar, P.; Varma, S.; Jain, S. L. J. Mater. Chem. A 2014, 2, 4514.
	(c) Nauth, A. M.; Schechtel, E.; Doren, R.; Tremel, W.; Opatz, T. J. Am. Chem. Soc. 2018, 140, 14169. doi: 10.1021/jacs.8b07539
[11]	For selected examples on other metal-catalyzed, see: pmid: 30998010
	(a) Singhal, S.; Jain, S. L.; Sain, B. Chem. Commun. 2009, 2371. pmid: 30998010
	(b) Zhang, Y.; Peng, H.; Zhang, M.; Cheng, Y.; Zhu, C. Chem. Commun. 2011, 47, 2354. doi: 10.1039/C0CC03844J pmid: 30998010
	(c) Sakai, N.; Mutsuro, A.; Ikeda, R.; Konakahara, T. Synlett 2013, 24, 1283. doi: 10.1055/s-00000083 pmid: 30998010
	(d) Lin, A.; Peng, H.; Abdukader, A.; Zhu, C. Eur. J. Org. Chem. 2013, 2013, 7286. doi: 10.1002/ejoc.v2013.32 pmid: 30998010
	(e) Yang, W.; Wei, L.; Yi, F.; Cai, M. Tetrahedron 2016, 72, 4059. doi: 10.1016/j.tet.2016.05.037 pmid: 30998010
	(f) Ping, Y.; Ding, Q.; Peng, Y. ACS Catal. 2016, 6, 5989. doi: 10.1021/acscatal.6b01632 pmid: 30998010
	(g) Liang, W.; Zhang, T.; Liu, Y.; Huang, Y.; Liu, Z.; Liu, Y.; Yang, B.; Zhou, X.; Zhang, J. ChemSusChem 2018, 11, 3586. doi: 10.1002/cssc.v11.20 pmid: 30998010
	(h) Patil, M. R.; Dedhia, N. P.; Kapdi, A. R.; Kumar, A. V. J. Org. Chem. 2018, 83, 4477. doi: 10.1021/acs.joc.8b00203 pmid: 30998010
	(i) Casado-Sanchez, A.; Uygur, M.; Gonzalez-Munoz, D.; Aguilar-Galindo, F.; Nova-Fernandez, J. L.; Arranz-Plaza, J.; Diaz-Tendero, S.; Cabrera, S.; Mancheno, O. G.; Aleman, J. J. Org. Chem. 2019, 84, 6437. doi: 10.1021/acs.joc.9b00520 pmid: 30998010
[12]	For selected examples on non-metal catalyzed, such as: AIBN, TBAI, TBHP, TBP, see:
	(a) Liu, L. H.; Wang, Z. K.; Fu, X. F.; Yan, C. H. Org. Lett. 2012, 14, 5692. doi: 10.1021/ol302708r
	(b) Zhang, C.; Liu, C.; Shao, Y.; Bao, X.; Wan, X. Chem.-Eur. J. 2013, 19, 17917. doi: 10.1002/chem.201303296
	(c) Wang, H.; Shao, Y.; Zheng, H.; Wang, H.; Cheng, J.; Wan, X. Chem.-Eur. J. 2015, 21, 18333. doi: 10.1002/chem.201502733
	(d) Zhang, Z.; Gu, K.; Bao, Z.; Xing, H.; Yang, Q.; Ren, Q. Tetrahedron 2017, 73, 3118. doi: 10.1016/j.tet.2017.04.033
	(e) Liu, P. Y.; Zhang, C.; Zhao, S. C.; Yu, F.; Li, F.; He, Y. P. J. Org. Chem. 2017, 82, 12786. doi: 10.1021/acs.joc.7b02021
	(f) Sun, M. X.; Wang, Y. F.; Xu, B. H.; Ma, X. Q.; Zhang, S. J. Org. Biomol. Chem. 2018, 16, 19717.
	(g) Ullah, B.; Zhou, Y.; Chen, J.; Bao, Z.; Yang, Y.; Yang, Q.; Ren, Q.; Zhang, Z. Tetrahedron Lett. 2019, 60, 348. doi: 10.1016/j.tetlet.2018.12.050
[13]	For selected examples on non-metal catalyzed, such as: PhIOAc₂ and AcOH, see:
	(a) Shu, X. Z.; Xia, X. F.; Yang, Y. F.; Ji, K. G.; Liu, X. Y.; Liang, Y. M. J. Org. Chem. 2009, 74, 7464. doi: 10.1021/jo901583r
	(b) Ueda, H.; Yoshida, K.; Tokuyama, H. Org. Lett. 2014, 16, 4194. doi: 10.1021/ol5018883
[14]	For selected examples on other non-metal catalyzed, see: pmid: 25147957
	(a) Rueping, M.; Zhu, S.; Koenigs, R. M. Chem. Commun. 2011, 47, 8679. doi: 10.1039/c1cc12907d pmid: 25147957
	(b) Allen, J. M.; Lambert, T. H. J. Am. Chem. Soc. 2011, 133, 1260. doi: 10.1021/ja109617y pmid: 25147957
	(c) Ushakov, D. B.; Gilmore, K.; Kopetzki, D.; McQuade, D. T.; Seeberger, P. H. Angew. Chem. Int. Ed. 2014, 53, 557. pmid: 25147957
	(d) Kabeshov, M. A.; Musio, B.; Murray, P. R.; Browne, D. L.; Ley, S. V. Org. Lett. 2014, 16, 4618. doi: 10.1021/ol502201d pmid: 25147957
	(e) Shen, H.; Zhang, X.; Liu, Q.; Pan, J.; Hu, W.; Xiong, Y.; Zhu, X. Tetrahedron Lett. 2015, 56, 5628. doi: 10.1016/j.tetlet.2015.08.058 pmid: 25147957
	(f) Orejarena Pacheco, J.C.; Lipp,, A.; Nauth,, A. M.; Acke,, F.; Dietz,, J. P.; Opatz,, T. Chem.-Eur. J. 2016, 22, 5409. doi: 10.1002/chem.201504845 pmid: 25147957
	(g) Fu, N.; Li, L.; Yang, Q.; Luo, S. Org. Lett. 2017, 19, 2122. doi: 10.1021/acs.orglett.7b00746 pmid: 25147957
	(h) Chen, W.; Ma, L.; Paul, A.; Seidel, D. Nat. Chem. 2018, 10, 165. doi: 10.1038/nchem.2871 pmid: 25147957
	(i) Periasamy, M.; Rao, G. Tetrahedron 2018, 74, 7209. doi: 10.1016/j.tet.2018.10.058 pmid: 25147957
[15]	For selected examples on other mediated catalyzed, see: pmid: 29707945
	(a) Wagner, A.; Ofial, A. R. J. Org. Chem. 2015, 80, 2848. doi: 10.1021/jo502846c pmid: 29707945
	(b) Wang, F.; Rafiee, M.; Stahl, S. S. Angew. Chem. Int. Ed. 2018, 57, 6686. doi: 10.1002/anie.v57.22 pmid: 29707945
	(c) Lennox, A. J. J.; Goes, S. L.; Webster, M. P.; Koolman, H. F.; Djuric, S. W.; Stahl, S. S. J. Am. Chem. Soc. 2018, 140, 11227. doi: 10.1021/jacs.8b08145 pmid: 29707945
	(d) Nutting, J. E.; Rafiee, M.; Stahl, S. S. Chem. Rev. 2018, 118, 4834. doi: 10.1021/acs.chemrev.7b00763 pmid: 29707945
[16]	(a) To, W. P.; Tong, G. S.; Lu, W.; Ma, C.; Liu, J.; Chow, A. L.; Che, C. M. Angew. Chem. Int. Ed. 2012, 51, 2654. doi: 10.1002/anie.201108080
	(b) Ushakov, D. B.; Gilmore, K.; Kopetzki, D.; McQuade, D. T.; Seeberger, P. H. Angew. Chem. Int. Ed. 2014, 53, 557.
	(c) Orejarena Pacheco, J.C.; Lipp,, A.; Nauth,, A. M.; Acke,, F.; Dietz,, J. P.; Opatz,, T. Chem.-Eur. J. 2016, 22, 5409. doi: 10.1002/chem.201504845
	(d) Nauth, A. M.; Lipp, A.; Lipp, B.; Opatz, T. Eur. J. Org. Chem. 2017, 2099.
	(e) Nauth, A. M.; Orejarena Pacheco, J. C.; Pusch, S.; Opatz, T. Eur. J. Org. Chem. 2017, 6966.
	(f) Nauth, A. M.; Schechtel, E.; Doren, R.; Tremel, W.; Opatz, T. J. Am. Chem. Soc. 2018, 140, 14169. doi: 10.1021/jacs.8b07539
	(g) Yi, B.; Yan, N.; Yi, N.; Xie, Y.; Wen, X.; Au, C.-T.; Lan, D. Chem.-Asian J. 2020, 15, 4302.
[17]	For selected reviews on electrochemical C—H functionalization, see:
	(a) Yang, Q.-L.; Fang, P.; Mei, T.-S. Chin. J. Chem. 2018, 36, 338. doi: 10.1002/cjoc.v36.4
	(b) Ma, C.; Fang, P.; Mei, T.-S. ACS. Catal. 2018, 8, 7179.
	(c) Yang, F.; Zhang, H.; Liu, X.; Wang, B.; Ackermann, L. Chin. J. Org. Chem. 2019, 39, 59. doi: 10.6023/cjoc201808017
	(d) Meng, Z.-Y.; Feng, C.-T.; Xu, K. Chin. J. Org. Chem. 2021, 41, 2535. (in Chinese) doi: 10.6023/cjoc202012013
	(蒙泽银, 冯承涛, 徐坤, 有机化学, 2021, 41, 2535.) doi: 10.6023/cjoc202012013
[18]	For selected reviews or highlights on electrochemistry, see:
	(a) Yan, M.; Kawamata, Y.; Baran, P. S. Chem. Rev. 2017, 117, 13230. doi: 10.1021/acs.chemrev.7b00397
	(b) Tang, S.; Liu, Y.; Lei, A. Chem 2018, 4, 27. doi: 10.1016/j.chempr.2017.10.001
	(c) Ma, H. X.; Mei, T. S. Chin. J. Org. Chem. 2020, 40, 3982. (in Chinese) doi: 10.6023/cjoc202000079
	(马红星, 梅天胜, 有机化学, 2020, 40, 3982.) doi: 10.6023/cjoc202000079
	(d) Jiang, Y.-Y.; Zeng, C.-C. Chin. J. Org. Chem. 2020, 40, 2999. (in Chinese) doi: 10.6023/cjoc202000057
	(蒋洋叶, 曾程初, 有机化学, 2020, 40, 2999.) doi: 10.6023/cjoc202000057
	(e) Ye, Z. H.; Zhang, F. Z. Chin. J. Org. Chem. 2020, 40, 241. (in Chinese) doi: 10.6023/cjoc202000002
	(叶增辉, 张逢质, 有机化学, 2020, 40, 241.) doi: 10.6023/cjoc202000002
	(f) Wang, X. Y.; Xu, X. T.; Wang, Z. H.; Fang, P.; Mei, T. S. Chin. J. Org. Chem. 2020, 40, 3738. (in Chinese) doi: 10.6023/cjoc202003022
	(王向阳, 徐学涛, 王振华, 方萍, 梅天胜, 有机化学, 2020, 40, 3738.) doi: 10.6023/cjoc202003022
[19]	(a) Shono, T.; Matsumura, Y.; Tsubata, K. J. Am. Chem. Soc. 1981, 103, 1172. doi: 10.1021/ja00395a029
	(b) Shono, T.; Matsumura, Y.; Uchida, K.; Tsubata, K.; Makino, A. J. Org. Chem. 1984, 49, 300. doi: 10.1021/jo00176a016
[20]	Gao, P. S.; Weng, X. J.; Wang, Z. H.; Zheng, C.; Sun, B.; Chen, Z. H.; You, S. L.; Mei, T. S. Angew. Chem. Int. Ed. 2020, 59, 15254. doi: 10.1002/anie.v59.35
[21]	(a) Steckhan, V. E. Angew. Chem. 1986, 98, 681. doi: 10.1002/(ISSN)1521-3757 pmid: 24500279
	(b) Ogibin, Y. N.; Elinson, M. N.; Nikishin, G. I. Russ. Chem. Rev. 2009, 78, 89. doi: 10.1070/RC2009v078n02ABEH003886 pmid: 24500279
	(c) Francke, R.; Little, R. D. Chem. Soc. Rev. 2014, 43, 2492. doi: 10.1039/c3cs60464k pmid: 24500279
[22]	(a) Quint, V.; Chouchène, N.; Askri, M.; Lalevée, J.; Gaumont, A.-C.; Lakhdar, S. Org. Chem. Front. 2019, 6, 41. doi: 10.1039/C8QO00985F pmid: 31525939
	(b) Huang, M.; Dai, J.; Cheng, X.; Ding, M. Org. Lett. 2019, 21, 7759. doi: 10.1021/acs.orglett.9b02707 pmid: 31525939
[23]	Rao, G. A.; Periasamy, M. Synthesis 2018, 50, 617. doi: 10.1055/s-0036-1590943
[24]	Yi, B.; Yan, N.; Yi, N.; Xie, Y.; Wen, X.; Au, C.-T.; Lan, D. RSC Adv. 2019, 9, 29721. doi: 10.1039/C9RA06120G
[25]	Wang, H. L.; Li, X. C.; Wu, F.; Wan, B. S. Tetrahedron Lett. 2012, 53, 681.
[26]	Lin, B. Z.; Shi, S. S.; Lin, R. C.; Cui, Y. Q.; Fang, M. J.; Tang, G.; Zhao, Y. F. J. Org. Chem. 2018, 83, 6754. doi: 10.1021/acs.joc.8b00674
[27]	Beke, D.; Bárczai, B. M.; Fcze, L. Chem. Ber. 1962, 95, 1054. doi: 10.1002/(ISSN)1099-0682

无金属参与的电化学促进2,2,6,6-四甲基哌啶-氮-氧化物(TEMPO)介导的环胺α-氰化和膦酰化反应

Electrochemical 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO)-Mediated α-Cyanation and Phosphonylation of Cyclic Amines with Metal-Free Conditions

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Entry	Variation from standard conditions	Yield^b/%
1	None	99 (97)^c
2	4-CN-TEMPO instead of TEMPO	71
3	4-COOH-TEMPO instead of TEMPO	48
4	ABNO instead of TEMPO	67
5	PhCO₂ABNO instead of TEMPO	42
6	Keto-ABNO instead of TEMPO	33
7	TBAOAc instead of TBAPF₆	46
8	TBAClO₄ instead of TBAPF₆	53
9	NaClO₄ instead of TBAPF₆	68
10	H₂O instead of CF₃CH₂OH	69
11	HFIP instead of CF₃CH₂OH	91
12	MeOH instead of CF₃CH₂OH	78
13	Isopropanol instead of CF₃CH₂OH	38
14	No current	N.R.
15	No TEMPO, no CH₃CH₂OH	29
16	No TEMPO	45

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[2]	Yuanlin Cai, Ya Lü, Guihua Nie, Zhichao Jin, Yonggui Chi. Recent Advances in the Synthesis of Cyanides Enabled by N-Heterocyclic Carbene Catalysis [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3135-3145.
[3]	Zhongrong Xu, Jieping Wan, Yunyun Liu. Transition Metal-Free C—H Thiocyanation and Selenocyanation Based on Thermochemical, Photocatalytic and Electrochemical Process [J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2425-2446.
[4]	Zhou Zhang, Yu Guo, Jing Yang, Dan Wu, Jiaxin Wang, Xinyue Hong, Peijun Cai, Liangce Rong. Electrochemically Promoted Halogenation of Imidazoland-[1,2-a]pyridine with Dichloro(bromo)ethylene and Iodoform [J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2104-2109.
[5]	Linlin Du, Hua Zhang. Photochemical and Electrochemical Borylation Involving Aryl and Alkyl Compounds [J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1726-1741.
[6]	Chuanchuan Wang, Zhiwei Ma, Xuehui Hou, Longhua Yang, Yajing Chen. Research and Application of N-Ts Cyanamides in Organic Synthesis [J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 74-93.
[7]	Wanjie Wei, Lei Zhan, Lei Gao, Guobao Huang, Xianli Ma. Research Progress of Electrochemical Synthesis of C-Sulfonyl Compounds [J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 17-35.
[8]	Yu Zheng, Shencheng Qian, Pengcheng Xu, Binnan Zheng, Shenlin Huang. Electrochemical Oxidative Thiocyanosulfonylation of Aryl Acetylenes [J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4275-4281.
[9]	Xiuying Li, Pingfang Tao, Yongyu Cheng, Qiong Hu, Weijuan Huang, Yun Li, Zhihui Luo, Guobao Huang. Recent Progress on the Electrochemical Difunctionalization of Alkenes/Alkynes [J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4169-4201.
[10]	Yingjie Liu, Zhichuan Wang, Jianping Meng, Chen Li, Kai Sun. Research Progress of Photoelectric Co-catalysis [J]. Chinese Journal of Organic Chemistry, 2022, 42(1): 100-110.
[11]	Zhe Chang, Jiaxin Wang, Xi Lu, Yao Fu. Synthesis of gem-Difluoroalkenes through Nickel-Promoted Electrochemical Reductive Cross-Coupling [J]. Chinese Journal of Organic Chemistry, 2022, 42(1): 147-159.
[12]	Jintao Wu, Zhongquan Liu. Advances in Free-Radical Promoted C(sp³)—C(sp³) Bond Conversion [J]. Chinese Journal of Organic Chemistry, 2022, 42(1): 16-32.
[13]	Yunshu Liu, Guodong Zhao, Wenju Wu, Yunze Wang, Yanchao Yu, Jun You, Bo Liu. Study on Asymmetric Conjugate Cyanation of 3,5-Dimethyl-N-α,β-unsaturated Acylpyrazole Catalyzed by Magnesium-Bisoxazoline Complex [J]. Chinese Journal of Organic Chemistry, 2022, 42(1): 208-217.
[14]	Xiang Liu, Wen Li, Canzhan Zhuang, Hua Cao. Application of Photochemical/Electrochemical Synthesis in C—H Functionalization of Quinoxalin-2(1H)-one [J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3459-3481.
[15]	Donglin Wang, Linglong Kan, Yudao Ma, Lei Liu. NaO^tBu-Catalyzed Hydrophosphonylation of δ-CN-δ-aryl-disubstituted para-Quinone Methides with Phosphine Oxides [J]. Chinese Journal of Organic Chemistry, 2021, 41(8): 3192-3203.