Synthesis of Alkylated Amides and Amines by Cu(OTf)2-Catalyzed N-Alkylation of Nitriles and Amines with Alcohols

doi:10.6023/cjoc201703028

Chin. J. Org. Chem. ›› 2017, Vol. 37 ›› Issue (8): 2034-2043.DOI: 10.6023/cjoc201703028 Previous Articles Next Articles

ARTICLE

Cu(OTf)₂催化腈和芳胺与醇的N-烷基化反应

马献涛^a,b, 李波^b, 肖映林^a, 余小春^b, 苏陈良^a,b, 徐清^a,b

a 深圳大学光电工程学院深圳大学-新加坡国大光电科技协同创新中心光电子器件与系统(教育部/广东省)重点实验室深圳 518060;
b 温州大学化学与材料工程学院温州 325035

收稿日期:2017-03-17 修回日期:2017-04-07 发布日期:2017-04-21
通讯作者: 余小春, 苏陈良, 徐清 E-mail:qing-xu@wzu.edu.cn;xiaochunyu@wzu.edu.cn;chmsuc@szu.edu.cn
基金资助:
国家自然科学基金（Nos.21672163，51502174，21302143）、浙江省自然科学杰出青年基金（No.LR14B020002）、中国博士后基金（No.2016M592520，2015M582401）资助项目.

Synthesis of Alkylated Amides and Amines by Cu(OTf)₂-Catalyzed N-Alkylation of Nitriles and Amines with Alcohols

Ma Xiantao^a,b, Li Bo^b, Xiao Yinglin^a, Yu Xiaochun^b, Su Chenliang^a,b, Xu Qing^a,b

a SZU-NUS Collaborative Innovation Center for Optoelectronic Science & Technology, Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Optoelectronic Engineering, Shenzhen University, Shenzhen 518060;
b College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035

Received:2017-03-17 Revised:2017-04-07 Published:2017-04-21
Contact: 10.6023/cjoc201703028 E-mail:qing-xu@wzu.edu.cn;xiaochunyu@wzu.edu.cn;chmsuc@szu.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 21672163, 51502174, 21302143), the Natural Science Foundation of Zhejiang Province for Distinguished Young Scholars (No. LR14B020002), and China Postdoctoral Science Foundation (2016M592520, 2015M582401).

1. Synthesis of Alkylated Amides and Amines by Cu(OTf)₂-Catalyzed N-Alkylation of Nitriles and Amines with Alcohols.PDF(2373KB)

Abstract

An efficient method for synthesis of the useful N-alkyl amides is achieved by a low loading Cu(OTf)₂-catalyzed Ritter reaction of nitriles with secondary alcohols and some primary alcohols. The same method can be extended to dehydrative N-alkylation of anilines with secondary alcohols to obtain N-alkylated anilines.

Key words: Alcohols, N-Alkylation, Amides, Amines, Copper Catalysis, Nitriles, Ritter Reaction

Cite this article

Ma Xiantao, Li Bo, Xiao Yinglin, Yu Xiaochun, Su Chenliang, Xu Qing. Synthesis of Alkylated Amides and Amines by Cu(OTf)₂-Catalyzed N-Alkylation of Nitriles and Amines with Alcohols[J]. Chin. J. Org. Chem., 2017, 37(8): 2034-2043.

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References

[1] (a) The AmideLinkage:Greenberg, A.; Breneman, C. M.; Liebman, J. F. Structural Significance in Chemistry, Biochemistry and Materials Science, John Wiley & Sons, New York, 2000.
(b) Johansson I. In Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 2, John Wiley & Sons, New York, 2004, 442.
[2] (a) Gunanathan, C.; Ben-David, Y.; Milstein, D. Science 2007, 317, 790.
(b) Ekoue-Kovi, K.; Wolf, C. Chem.-Eur. J. 2008, 14, 6302.
(c) Allen, C. L.; Williams, J. M. Chem. Soc. Rev. 2011, 40, 3405.
(d) García-Álvarez, R.; Crochet, P.; Cadierno, V. Green Chem. 2013, 15, 46.
(e) Crochet, P.; Cadierno, V. Chem. Commun. 2015, 51, 2495.
(f) Watson, A. J.; Williams, J. M. Science 2010, 329, 635.
(g) Nixon, T. D.; Whittlesey, M. K.; Williams, J. M. Dalton Trans. 2009, 38, 753.
(h) Guillena, G.; Ramón, D. J.; Yus, M. Chem. Rev. 2010, 110, 1611.
(i) Suzuki, T. Chem. Rev. 2011, 111, 1825.
(j) Bähn, S.; Imm, S.; Neubert, L.; Zhang, M.; Neumann, H.; Beller, M. ChemCatChem 2011, 3, 1853.
(k) Yang, Q.; Wang, Q.; Yu, Z. Chem. Soc. Rev. 2015, 44, 2305.
[3] For reviews:(a) Ma, X.; Su, C.; Xu, Q. N-Alkylation by Hydrogen autotransfer Reactions in Hydrogen Transfer Reactions:Reductions and Beyond, Eds.:Guillena, G.; Ramón, D. J. Top. Curr. Chem. 2016, 374(27), 1.
(b) Xu, Q.; Li, Q. Chin. J. Org. Chem. 2013, 33, 18(in Chinese). (徐清, 李强, 有机化学, 2013, 33, 18.) For reports:
(c) Feng, S. L.; Liu, C. Z.; Li, Q.; Yu, X. C.; Xu, Q. Chin. Chem. Lett. 2011, 22, 1021.
(d) Liu, C.; Liao, S.; Li, Q.; Feng, S.; Sun, Q.; Yu, X.; Xu, Q. J. Org. Chem. 2011, 76, 5759.
(e) Yu, X.; Liu, C.; Jiang, L.; Xu, Q. Org. Lett. 2011, 13, 6184.
(f) Li, Q.; Fan, S.; Sun, Q.; Tian, H.; Yu, X.; Xu, Q. Org. Biomol. Chem. 2012, 10, 2966.
(g) Yu, X.; Jiang, L.; Li, Q.; Xie, Y.; Xu, Q. Chin. J. Chem. 2012, 30, 2322.
[4] We have also engaged in the synthesis of carboxamides from nitriles, see:(a) Chen, H.; Dai, W.; Chen, Y.; Xu, Q.; Chen, J.; Yu, L.; Zhao, Y.; Ye, M.; Pan, Y. Green Chem. 2014, 16, 2136.
(b) Li, Y.; Chen, H.; Liu, J.; Wan, X.; Xu, Q. Green Chem. 2016, 18, 4825.
[5] (a) Ritter, J. J.; Kalish, J. J. Am. Chem. Soc. 1948, 70, 4048.
(b) Plaut, H.; Ritter, J. J. J. Am. Chem. Soc. 1951, 73, 4076.
[6] For reviews, see:(a) Guérinot, A.; Reymond, S.; Cossy, J. Eur. J. Org. Chem. 2012, 19.
(b) Jiang, D.; He, T.; Ma, L.; Wang, Z. RSC Adv. 2014, 4, 64936. For reports, see:
(c) Reddy, K. L. Tetrahedron Lett. 2003, 44, 1453.
(d) Shi, M. Tian, G. Q. Tetrahedron Lett. 2006, 47, 8059.
(e) Sanz, R.; Martínez, A.; Guilarte, V.; Álvarez-Gutiérrez, J. M.; Rodríguez, F. Eur. J. Org. Chem. 2007, 4642.
(f) Barbero, M.; Bazzi, S.; Cadamuro, S. Eur. J. Org. Chem. 2009, 3, 430.
(g) Firouzabadi, H.; Sardarian, A. R.; Badpava, H. Synth. Commun. 1994, 24, 601.
(h) Callen, E.; Burton, A. J.; Barrett, A. G. M. Tetrahedron Lett. 2006, 47, 8699.
(i) Anxionnat, B.; Guerinot, A.; Reymond, S.; Cossy, J. Tetrahedron Lett. 2009, 50, 3470.
(j) Jefferies, L. R.; Cook, S. P. Tetrahedron 2014, 70, 4204.
(k) Theerthagiri, P. Lalitha, A.; Arunachalam, P. N. Tetrahedron Lett. 2010, 51, 2813.
(l) Yaragorla, S.; Singh, G.; Saini, P. L.; Reddy, M. K. Tetrahedron Lett. 2014, 55, 4657.
(m) Posevins, D.; Suta, K.; Turks, M. Eur. J. Org. Chem. 2016, 1414.
(n) Yamato, T.; Hu, J. Y.; Sbinoda, N. J. Chem. Res. 2007, 11, 641.
(o) Mesquita, L. M.; Pinto, R. M.; Salvador, J. A.; Clark, J. H.; Budarin, V. L. Catal. Commun. 2015, 69, 170.
(p) Ibrahim, N.; Hashmi, A. S. K.; Rominger, F. Adv. Synth. Catal. 2011, 353, 461.
(q) Dokli, I.; Gredi?ak, M. Eur. J. Org. Chem. 2015, 2727.
(r) Khaksara, S.; Fattahia, E.; Fattahib, E. Tetrahedron Lett. 2011, 52, 5943.
(s) Singh, G; Dada, R; Yaragorla, S. Tetrahedron Lett. 2016, 57, 4424.
[7] We previously found Cu(OAc)2 is an efficient catalyst for alkylation reactions, see:Ref.[3f] and Liao, S.; Yu, K.; Li, Q.; Tian, H.; Zhang, Z.; Yu, X.; Xu, Q. Org. Biomol. Chem. 2012, 10, 2973.
[8] Lepore and co-workers reported an indirect Cu-catalyzed reaction of nitriles with secondary cycloalkanols, in which up to 20 mol% of Cu catalyst was used and excess amounts of SO₂Cl₂ was required to activate the alcohols into the corresponding alkyl chlorosulfites. See:Al-huniti, M. H.; Lepore, S. D. Adv. Synth. Catal. 2013, 355, 3071.
[9] Theerthagiri, P.; Lalitha, A.; Arunachalam, P. N. Tetrahedron Lett. 2010, 51, 2813.
[10] Crampton, R.; Woodward, S.; Fox, M. Adv. Synth. Catal. 2011, 353, 903.
[11] Zhang, X.; Huang, K.; Hou, G.; Cao, B.; Zhang, X. Angew. Chem. Int. Ed. 2010, 49, 6421.
[12] Stavbera, G.; Zupana, M.; Stavber, S. Tetrahedron Lett. 2006, 47, 8463.
[13] Lakouraj, M. M.; Mokhtary, M. Monatsh Chem. 2009, 140, 53.
[14] Shakeri, M. S.; Tajik, H.; Niknam, K. J. Chem. Sci. 2012, 124,1025.
[15] Lakouraj, M. M.; Mokhtary, M. Monatsh. Chem. 2009, 140, 53.
[16] Britton, J.; Chalker, J. M.; Raston, C. L. Chem.-Eur. J. 2015, 21, 10660.
[17] Jamieson, C.; Congreve, M. S.; Emiabata-Smith, D. F.; Ley, S. V. Synlett 2000, 1603.
[18] Yu, J.; Wu, Y. J.; Cheng, B. L.; Wei, K.; Li. J. Y. Adv. Synth. Catal. 2009, 351, 767.
[19] Zhu, A.; Li, L.; Wang, J.; Zhuo, K. Green Chem. 2011, 13, 1244.
[20] Strekowski, L.; Cegla, M. T.; Harden, D. B.; Kong, S.-B. J. Org. Chem. 1989, 54, 2464.
[21] Cui, X.; Dai, X.; Deng, Y.; Shi, F. Chem.-Eur. J. 2013, 19, 3665.

Cu(OTf)₂催化腈和芳胺与醇的N-烷基化反应

Synthesis of Alkylated Amides and Amines by Cu(OTf)₂-Catalyzed N-Alkylation of Nitriles and Amines with Alcohols

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Cu(OTf)2催化腈和芳胺与醇的N-烷基化反应