10.1002/cssc.201701299
ChemSusChem
COMMUNICATION
amines to N-substituted-5-methyl-2-pyrrolidones. This catalytic
system operates at low catalyst loading and hydrogen pressure
under neat conditions. This catalyst efficiently transforms a
variety of amines including very bulky and functional ones. The
catalytic system is also applicable to synthesis N-
arylisoindolinone derivatives. This mild and green catalytic
system provides a general protocol for converting biomass-
based chemicals into value added products.
Acknowledgements
The authors acknowledge the China Scholarship Council for a
grant to SW.
Keywords: biomass• levulinic acid• pyrrolidones• reductive
amination• iridium
[1]
a) J. R. Rostrup-Nielsen, Science 2005, 308, 1421-1422; b) G. W.
Huber, S. Iborra, A. Corma, Chem. Rev. 2006, 106, 4044-4098; c) A.
Corma, S. Iborra, A. Velty, Chem. Rev. 2007, 107, 2411-2502; d) P.
Gallezot, Catal. Today 2007, 121, 76-91; e) L. D. Schmidt, P. J.
Dauenhauer, Nature, 2007, 447, 914-915; f) G. Yong, Y. Zhang, J. Y.
Ying, Angew. Chem. Int. Ed. 2008, 47, 9345-9348; g) J. J. Bozell, G. R.
Petersen, Green Chem. 2010, 12, 539-554; h) J. C. Serrano-Ruiz, J. A.
Dumesic, Energy Environ. Sci. 2011, 4, 83-99; i) P. Gallezot, Chem.
Soc. Rev. 2012, 41, 1538-1558.
Experimental Section
Levulinic acid (98%), amines and 2-formylbenzoic acid were purchased
from Sigma-Aldrich and used as received. Solvents (methanol, diethyl
ether, water) were HPLC grade and used as received. Ir1 was
synthesized according to a reported procedure.[20] NMR spectra were
recorded on Bruker Avance (300 MHz or 400 MHz) instruments.
[2]
a) B. Kamm, Angew. Chem. Int. Ed. 2007, 46, 5056-5058; b) D. M.
Alonso,S. G. Wettsteina, J. A. Dumesic, Chem. Soc. Rev. 2012, 41,
8075-8098; c) R.-J. van Putten, J. C. van der Waal, Ed de Jong, C. B.
Rasrendra, H. J. Heeres, J. G. de Vries, Chem. Rev. 2013, 113, 1499-
1597; d) A.Farrán, C. Cai, M. Sandoval, Y. Xu, J. Liu, M. J. Hernáiz, R.
J. Linhardt, Chem. Rev. 2015, 115, 6811-6853; e) C. Li, X. Zhao, A.
Wang, G. W. Huber, T. Zhan, Chem. Rev. 2015, 115, 11559-11624; f)
T. Werpy, G. R. Petersen, Top Value Added Chemicals from Biomass.
Volume I - Results of Screening for Potential Candidates from Sugars
and Synthesis Gas, U. S. D. o. Energy, 2004. g) J. J. Bozell, G. R.
Petersen, Green Chem. 2010, 12, 539-554.
General procedure for the reductive amination of LA: Amine (2 mmol), Ir1
(0.05-0.1mol%), levulinic acid (2 mmol) were placed in a 20 ml autoclave.
The reactor was flushed with H2 and then pressurized with 5 bar of H2
under stirring. Once the required pressure was reached, the reactor was
maintained connected for an additional 2 minutes before closing. The
mixture was stirred at the appropriate temperature for the desired time.
The reactor was cooled down and carefully depressurized. The reaction
mixture was analyzed by 1HNMR and directly purified by flash column
chromatography using petroleum ether and ethyl acetate with 1 vol%
triethylamine as eluent.
[3]
a) Y. Isoda; M. Azuma, Japanese Patent 08053390, 1994; b) L. E.
Manzer, U.S. Patent 6743819 B1, 2004; c) L. E. Manzer, U.S. Patent
2006/247443A1, 2006.
General procedure for the sequential dehydration/reductive amination
from glucose: (0.45 g, 2.5 mmol) was loaded into a 20 mL autoclave, and
H2SO4 (2.5 mL, 0.5 mol/L) was added. The autoclave was quickly heated
to 170 oC, and vigorously stirred for 2 h at the same temperature. The
reaction mixture was allowed to cool to room temperature before addition
[4]
[5]
X.-Y. Liu, C.-H. Li, C.-M. Che, Org. Lett. 2006, 8, 2707-2710
J. Davies, T. D. Svejstrup, D. Reina, N.S. Sheikh, D. Leonori, J. Am.
Chem. Soc. 2016, 138, 8092−8095.
[6]
M.-C. Fu, R. Shang, W.-M. Cheng, Y. Fu, Angew. Chem. Int. Ed. 2015,
of
a 1M sodium bicarbonate solution until pH 7. Insoluble solid
54, 9042-9046.
byproducts were removed by filtration. The hydrolysis filtrate was
transferred to a 20 mL autoclave containing the desired amount of
catalyst Ir1 (0.05 mol%) and aniline (1 equiv.). The reactor was heated in
an oil bath at 110 °C with 20 bar H2 for 16 h. The reactor was allowed to
cool down to room temperature and carefully depressurized. The reaction
mixture was extracted with dichloromethane (3 x 5 mL). The combined
organic phases were evaporated to dryness and the crude product was
purified by column chromatography on silica gel using petroleum ether /
ethyl acetate (3/1; v/v) as eluent.
[7]
[8]
R. L. Frank, W. R. Schmitz, B. Zeidman, Org. Synth. 1947, 27, 28.
a) L. E. Manzer, F. E. Herkes, US Patent 2004192933, 2003; b) L. E.
Manzer, WO Pat, 2004084633, 2004.
[9]
X. L. Du, L. He, S. Zhao, Y. M. Liu, Y. Cao, H. Y. Heand, K. N. Fan,
Angew. Chem. Int. Ed. 2011, 50, 7815-7819.
[10] J. Zhang, B. Xie, L. Wang, X. Yi, C. Wang, G. Wang, Z. Dai, A. Zheng,
F.-S. Xiao, ChemCatChem DOI: 10.1002/cctc.201600739.
[11] A. S. Touchy, S. M. A. H. Siddiki, K. Kon, K.-i. Shimizu, ACS Catal.
2014, 4, 3045−3050
[12] a) G. Chieffi, M. Braun, D. Esposito, ChemSusChem, 2015, 8, 3590-
3594; b) C. Ortiz-Cervantes, M. Flores-Alamo, J. J. García,
Tetrahedron Lett. 2016, 57, 766–771; c) J. D. Vidal, M. J. Climent, A.
Corma, D. P. Concepcion, S. Iborra, ChemSusChem 2017, 10, 119-128;
d) Z. Sun, J. Chen, T. Tu, Green Chem. 2017, 19, 789-794; e) T. Zhang,
Y. Ge, X. Wang, J. Chen, X. Huang, Y. Liao, ACS Omega 2017, 2,
3228-3240; f) G. Gao, P. Sun, Y. Li, F. Wang, Z. Zhao, Y. Qin, F. Li,
ACS Catal. 2017, 7, 4927-4935.
General procedure for the reductive amination of 2-formylbenzoic acid:
Amine (2 mmol), Ir1 (0.05 mol%) and 2-formylbenzoic acid (2 mmol)
were placed in a 20 ml autoclave. The reactor was flushed with H2 and
then pressurized with 5 bar of H2 under stirring. Once the required
pressure was reached, the reactor was maintained connected for an
additional 2 minutes before closing. The mixture was stirred at the
appropriate temperature for the desired time. The reactor was cooled
down and carefully depressurized. The product was directly purified by
flash column chromatography using petroleum ether and ethyl acetate
with 1 vol% triethylamine as eluent.
[13] Y. B. Huang, J. J. Dai, X. J. Deng, Y. C. Qu, Q. X. Guo, Y. Fu,
ChemSusChem, 2011, 4, 1578–1581.
[14] Y. Wei, C. Wang, X. Jiang, D. Xue, J. Li, J. Xiao, Chem. Commun.
2013,49, 5408–5410;
General procedure for the C-H arylation: 2-phenylprydine (0.078 g, 0.5
mmol), chlorobenzene (0.14 g, 1.25 mmol), [RuCl2(p-cymene)]2 (0.0077g,
0.0125 mmol), K2CO3 (0.207 g, 1.5 mmol) and NMP or 2b (1.5 mL) were
added to a Schlenk tube under an argon atmosphere. The resulting
mixture was stirred at 120 °C for 2 h. The reaction media was cooled
down and filtrated over Celite. The crude mixture was analyzed by 1H
NMR.
[15] Z. Xu, P. Yan, H. Jiang, K. Liu, Z. C. Zhang, Chin. J. Chem. 2017, 35,
581-585
[16] a) Y. Ogiwara, T. Uchiyama, N. Sakai, Angew. Chem. Int. Ed. 2016, 55,
1864-1867; b) C. Wu, X. Luo, H. Zhang, X. Liu, G. Ji, Z. Liu, Z. Liu,
Green Chem. 2017, DOI: 10.1039/C7GC00999B;
[17] A. Ledoux, L. S. Kuigwa, E. Framery, B. Andrioletti, Green Chem. 2015,
17, 3251-3254
This article is protected by copyright. All rights reserved.