One-Pot Synthesis of N-Arylated Amines by Hydroaminomethyl­ation of 2,5-Dihydrofuran with Aromatic Amines

Zhiwen Zheng; Lailai Wang

doi:10.1055/s-0037-1610681

Synthesis, Inhaltsverzeichnis

Synthesis 2019; 51(07): 1585-1594
DOI: 10.1055/s-0037-1610681

paper

One-Pot Synthesis of N-Arylated Amines by Hydroaminomethylation of 2,5-Dihydrofuran with Aromatic Amines

Zhiwen Zheng

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, P. R. of China eMail: wll@licp.cas.cn

^bUniversity of Chinese Academy of Sciences, Beijing 100039, P. R. of China eMail: zhengzhiwen@licp.cas.cn

,

Lailai Wang*

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, P. R. of China eMail: wll@licp.cas.cn

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

A new efficient catalytic system for one-step synthesis of N-arylated amines, for example, an important intermediate, 4-ethyl-N-[(tetrahydrofuran-3-yl)methyl]aniline, is achieved by using different rhodium precursor and phosphorus ligands catalyzed hydroaminomethylation of aniline and its derivatives with heterocyclic and/or cyclic olefins. By screening the reaction parameters, the optimal reaction conditions are found as follows: methanol as a solvent, PPh₃ as a ligand, [Rh(cod)₂]BF₄ as a catalyst precursor, a P/Rh ratio of 5:1, syngas pressure 4 MPa (H₂/CO = 3:1), 100 °C, 20 hours, and no additives. The conversion of aniline reaches >99% and the yield of N-[(tetrahydrofuran-3-yl)methyl]aniline is up to 99% using this catalytic system. Moreover, the reaction of aniline and various cyclic olefins is investigated under the optimal conditions, and excellent conversion and good yields are obtained.

Key words

heterocyclic olefins - cyclic olefins - hydroaminomethylation - amines - phosphine/Rh - 2,5-dihydrofuran

Volltext

Referenzen

References

1a Yamamoto Y, Radhakrishnan U. Chem. Soc. Rev. 1999; 28: 199
1b Helmchen G, Dübon P, Farwick A. Synlett 2009; 1413
1c Etayo P, Vidal-Ferran A. Chem. Soc. Rev. 2013; 42: 728
1d Müller TE, Beller M. Chem. Rev. 1998; 98: 675
1e Zhu GD, Gandhi VB, Gong J, Thomas S, Luo Y, Liu X, Shi Y, Klinghofer V, Johnson EF, Frost D, Donawho C, Jarvis K, Bouska J, Marsh KC, Rosenberg SH, Giranda VL, Penning TD. Bioorg Med. Chem. Lett. 2008; 18: 3955
1f Zhang M, Tamiya J, Nguyen L, Rowbottom MW, Dyck B, Vickers TD, Grey J, Schwarz DA, Heise CE, Haelewyn J, Mistry MS, Goodfellow VS. Bioorg Med. Chem. Lett. 2007; 17: 2535

2 Teleha C, Johnson E, Hubieki M, Combs A. Synthesis 2011; 4023

3a Clerici A, Cannella R, Panzeri W, Pastori N, Regolini E, Porta O. Tetrahedron Lett. 2005; 46: 8351
3b Angelovski G, Eilbracht P. Tetrahedron 2003; 59: 8265
3c Fuentes JA, Wawrzyniak P, Roff GJ, Bühl M, Clarke ML. Catal. Sci. Technol. 2011; 1: 431

4a Quach TD, Batey RA. Org. Lett. 2003; 5: 4397
4b Antilla JC, Buchwald SL. Org. Lett. 2001; 3: 2077

5 Ahmed M, Seayad AM, Jackstell R, Beller M. J. Am. Chem. Soc. 2003; 125: 10311

6a Chen C, Dong X.-Q, Zhang X. Org. Chem. Front. 2016; 3: 1359
6b Vanbésien T, Monflier E, Hapiot F. Green Chem. 2017; 19: 1940
6c Fleischer I, Gehrtz P, Hirschbeck V, Ciszek B. Synthesis 2016; 48: 1573
6d Vieira TO, Alper H. Org. Lett. 2008; 10: 485

7a Crozet D, Urrutigoïty M, Kalck P. ChemCatChem 2011; 3: 1102
7b Villa-Marcos B, Xiao J. Chin. J. Catal. 2015; 36: 106
7c Routaboul L, Buch C, Klein H, Jackstell R, Beller M. Tetrahedron Lett. 2005; 46: 7401

8 Reppe W, Vetter H. Justus Liebigs Ann. Chem. 1953; 582: 133
9 Rische T, Kitsos-Rzychon B, Eilbracht P. Tetrahedron 1998; 54: 2723
10 Seayad AM, Selvakumar K, Ahmed M, Beller M. Tetrahedron Lett. 2003; 44: 1679
11 Okuro K, Alper H. Tetrahedron Lett. 2010; 51: 4959
12 Li S, Huang K, Zhang J, Wu W, Zhang X. Org. Lett. 2013; 15: 3078
13 Li S, Huang K, Zhang J, Wu W, Zhang X. Org. Lett. 2013; 15: 1036
14 Faßbach TA, Gaide T, Terhorst M, Behr A, Vorholt AJ. ChemCatChem 2017; 9: 1359
15 Beigi M, Ricken S, Müller KS, Koç F, Eilbracht P. Eur. J. Org. Chem. 2011; 1482

16a Chen C, Jin S, Zhang Z, Wei B, Wang H, Zhang K, Lv H, Dong XQ, Zhang X. J. Am. Chem. Soc. 2016; 138: 9017
16b Yan Y, Zhang X, Zhang X. J. Am. Chem. Soc. 2006; 128: 16058
16c Liu J, Kubis C, Franke R, Jackstell R, Beller M. ACS Catal. 2016; 6: 907

17a Vorholt AJ, Immohr S, Ostrowski KA, Fuchs S, Behr A. Eur. J. Lipid Sci. Technol. 2017; 119: 1600211
17b Behr A, Wintzer A. Chem. Eng. Technol. 2015; 38: 2299

18 Crozet D, Kefalidis CE, Urrutigoïty M, Maron L, Kalck P. ACS Catal. 2014; 4: 435

19a Liu G, Huang K, Cai C, Cao B, Chang M, Wu W, Zhang X. Chem. Eur. J. 2011; 17: 14559
19b Oliveira KC. B, Carvalho SN, Duarte MF, Gusevskaya EV, dos Santos EN, Karroumi JE, Gouygou M, Urrutigoïty M. Appl. Catal., A 2015; 497: 10
19c Meng J, Li XH, Han ZY. Org. Lett. 2017; 19: 1076
19d Dutta B, Schwarz R, Omar S, Natour S, Abu-Reziq R. Eur. J. Org. Chem. 2015; 1961
19e Seidensticker T, Vosberg JM, Ostrowski KA, Vorholt AJ. Adv. Synth. Catal. 2016; 358: 610

20 Gervais N. Patent Appl. WO 2017013496, 2017
21 Lapidus AL, Brezhnev LY, Vartanyan MM, Solov’eva TY, Vol’f EY. Izv. Akad. Nauk SSSR, Ser. Khim. 1989; 1198
22 Chen C, Dong X.-Q, Zhang X. Org. Chem. Front. 2016; 3: 1359

Zusatzmaterial

Supporting Information

One-Pot Synthesis of N-Arylated Amines by Hydroaminomethyl­ation of 2,5-Dihydrofuran with Aromatic Amines

One-Pot Synthesis of N-Arylated Amines by Hydroaminomethylation of 2,5-Dihydrofuran with Aromatic Amines