Activation of Primary Amines by Copper(I)-Based Lewis Acid Promoters in the Solventless Synthesis of Secondary Propargylamines

Cristina Cimarelli; Federica Navazio; Federico V. Rossi; Fabio Del Bello; Enrico Marcantoni

doi:10.1055/s-0037-1612253

Synthesis, Table of Contents

Synthesis 2019; 51(11): 2387-2396
DOI: 10.1055/s-0037-1612253

paper

Activation of Primary Amines by Copper(I)-Based Lewis Acid Promoters in the Solventless Synthesis of Secondary Propargylamines

Cristina Cimarelli *

^aSchool of Science and Technology, Chemistry Division, University of Camerino, Via S. Agostino 1, 62032 Camerino, Italy Email: cristina.cimarelli@unicam.it

,

Federica Navazio

^aSchool of Science and Technology, Chemistry Division, University of Camerino, Via S. Agostino 1, 62032 Camerino, Italy Email: cristina.cimarelli@unicam.it

,

Federico V. Rossi

^aSchool of Science and Technology, Chemistry Division, University of Camerino, Via S. Agostino 1, 62032 Camerino, Italy Email: cristina.cimarelli@unicam.it

,

Fabio Del Bello

^bSchool of Pharmacy, Medicinal Chemistry Unit, University of Camerino, Via S. Agostino 1, 62032 Camerino, Italy

,

Enrico Marcantoni

^aSchool of Science and Technology, Chemistry Division, University of Camerino, Via S. Agostino 1, 62032 Camerino, Italy Email: cristina.cimarelli@unicam.it

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Abstract

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Abstract

Primary amines are activated by copper(I)-based Lewis acid promoters in an A³-coupling one-pot solventless reaction with aldehydes and phenylacetylene for the synthesis of secondary propargylamines. The reaction is promoted by a CuSO₄/NaI system, a practical precursor of the in situ generated effective CuI/I₂ system, that worked well, but only in a restricted number of examples. Substitution of I₂ with CeCl₃·7H₂O in a one-pot two-step reaction provided good yields and a wider applicability, with the added value given by a safer procedure.

Key words

propargylamines - A³ coupling - primary amines - copper - cerium trichloride - Lewis acids

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References

References
1 Ermolat’ev DS, Bariwal JB, Steenackers HP. L, De Keersmaecker SC. J, Van der Eycken EV. Angew. Chem. Int. Ed. 2010; 49: 9465
2 Fedoseev P, Sharma N, Khunt R, Ermolat’ev DS, Van der Eycken EV. RSC Adv. 2016; 6: 75202
3 Yuan B, Zhang F, Li Z, Yang S, Yan R. Org. Lett. 2016; 18: 5928
4 Weng J, Chen Y, Yue B, Xu M, Jin H. Eur. J. Org. Chem. 2015; 3164
5 Kwon K.-H, Serrano CM, Koch M, Barrows LR, Looper RE. Org. Lett. 2014; 16: 6048
6 Grishina AA, Polyakova SM, Kunetskiy RA, Císařová I, Lyapkalo IM. Chem. Eur. J. 2011; 17: 96
7 Ranjan A, Yerande R, Wakchaure PB, Yerande SG, Dethe DH. Org. Lett. 2014; 16: 5788
8 Nechaev AA, Peshkov AA, Van Hecke K, Peshkov VA, Van der Eycken EV. Eur. J. Org. Chem. 2017; 1063
9 Ying J, Wang H, Qi X, Peng J, Wu X. Eur. J. Org. Chem. 2018; 688
10 Wang H, Ying J, Lai M, Qi X, Peng J, Wu X. Adv. Synth. Catal. 2018; 360: 1693
11 Peshkov VA, Pereshivko OP, Sharma S, Meganathan T, Parmar VS, Ermolat’ev DS, Van der Eycken EV. J. Org. Chem. 2011; 76: 5867
12 Pereshivko OP, Peshkov VA, Jacobs J, Van Meervelt L, Van der Eycken EV. Adv. Synth. Cat. 2013; 355: 781
13 Campbell MJ, Toste FD. Chem. Sci. 2011; 2: 1369
14 Wang G, Liu C, Li B, Wang Y, Van Hecke K, Van der Eycken EV, Pereshivko OP, Peshkov VA. Tetrahedron 2017; 73: 6372; and references cited therein
15 Pereshivko OP, Peshkov VA, Peshkov AA, Jacobs J, Van Meervelt L, Van der Eycken EV. Org. Biomol. Chem. 2014; 12: 1741
16 Sadeghzadeh SM, Zhiani R, Emrani S. Appl. Organomet. Chem. 2018; 32: e3941
17 Sadeghzadeh SM. Appl. Organomet. Chem. 2016; 30: 835
18 Sadeghzadeh SM. J. Mol. Catal. A: Chem. 2016; 423: 216
19 Liu X, Wang MY, Wang SY, Wang Q, He LN. ChemSusChem 2017; 10: 1210
20 Kikuchi S, Yoshida S, Sugawara Y, Yamada W, Cheng H, Fukui K, Sekine K, Iwakura I, Ikeno T, Yamada T. Bull. Chem. Soc. Jpn. 2011; 84: 698
21 Zhao Y, Qiu J, Li Z, Wang H, Fan M, Wang J. ChemSusChem 2017; 10: 2001
22 Hu J, Ma J, Zhu Q, Zhang Z, Wu C, Han B. Angew. Chem. Int. Ed. 2015; 54: 5399
23 Wang M, Song Q, Ma R, Xie J, He L. Green Chem. 2016; 18: 282
24 Hu J, Ma J, Zhang Z, Zhu Q, Zhou H, Lua W, Han B. Green Chem. 2015; 17: 1219
25 Li CJ, Wei C. Chem. Commun. 2002; 268
26 Peshkov VA, Pereshivko OP, Van der Eycken EV. Chem. Soc. Rev. 2012; 41: 3790; and references cited therein
27 Lauder K, Toscani A, Scalacci N, Castagnolo D. Chem. Rev. 2017; 117: 14091 ; and references cited therein
28 Saha TK, Das R. ChemistrySelect 2018; 3: 147
29 Shehzadi SA, Saeed A, Lemière F, Maes BU. W, Tehrani KA. Eur. J. Org. Chem. 2018; 78
30 Yusubov MS, Zhdankin VV. Resour.-Effic. Technol. 2015; 1: 49
31 Küpper FC, Feiters MC, Olofsson B, Kaiho T, Yanagida S, Zimmermann MB, Carpenter LJ, Luther GV. III, Lu Z, Jonsson M, Kloo L. Angew. Chem. Int. Ed. 2011; 50: 11598
32 Li X, Mao Z, Wang Y, Chen W, Lin X. Tetrahedron 2011; 67: 3858
33 Brotherton WS, Clark RJ, Zhu L. J. Org. Chem. 2012; 77: 6443 ; and references cited therein
34 Bailey AD, Cherney SM, Anzalone PW, Anderson ED, Ernat JJ, Mohan RJ. Synlett 2006; 215
35 Bartoli G, Marcantoni E, Marcolini M, Sambri L. Chem. Rev. 2010; 110: 6104 ; and references cited therein
36 Multicomponent Reactions: Concepts and Applications for Design and Synthesis. Herrera RP, Marqués-López E. John Wiley & Sons; Hoboken, New Jersey: 2015
37 Bartoli G, Marcantoni E, Sambri L. Synlett 2003; 2101
38 Bartoli G, Fernández-Bolaños JG, Di Antonio G, Foglia G, Giuli S, Gunnella R, Mancinelli M, Marcantoni E, Paoletti M. J. Org. Chem. 2007; 72: 6029
39 Cimarelli C, Di Nicola M, Diomedi S, Giovannini R, Hamprecht D, Properzi R, Sorana F, Marcantoni E. Org. Biomol. Chem. 2015; 13: 11687
40 Ravishankar L, Patwe SA, Gosarani N, Roy A. Synth. Commun. 2010; 40: 3177
41 Siemsen P, Livingston RC, Diederich F. Angew. Chem. Int. Ed. 2000; 39: 2632
42 Lu Y, Johnstone TC, Arndtsen BA. J. Am. Chem. Soc. 2009; 131: 11284
43 Feng H, Ermolat’ev DS, Song G, Van der Eycken EV. J. Org. Chem. 2011; 76: 7608
44 Wachenfeldt H. v, Paulsen F, Sundin A, Strand D. Eur. J. Org. Chem. 2013; 4578
45 Bariwal JB, Ermolat’ev DS, Van der Eycken EV. Chem. Eur. J. 2010; 16: 3281
46 Tong S, Wang Q, Wang MX, Zhu J. Angew. Chem. Int. Ed. 2015; 54: 1293
47 Shi L, Tu YQ, Wang M, Zhang FM, Fan CA. Org. Lett. 2004; 6: 1001

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