ACS Catalysis
Letter
a
Table 4. Statistical Calculation and Experimental Results
data resource
GC-MS
D1−N m/z = 100
D2−N m/z = 101
D3−N m/z = 102
D4−N m/z = 103
5.8%
70.1%
20.8%
2.7%
calcd (path A, Scheme 2)
calcd (path B, Scheme 2)
0.2%< ω <2.5%
4.7%
6.9%<ω <38.9%
70.7%
46.8%< ω <69.4%
24.5%
11.7%< ω <23.5%
0%
a
Reaction conditions: DHMF (0.5 mmol), catalyst (0.00125 mmol, 0.25 mol % to DHMF), and D2O (2.0 mL), under 10 bar of H2, at 120 °C, for
0.5 h.
evident that the calculated data based on path B and the
experimental data agree well. Thus, the calculated data support
that the formation of HHD from DHMF is mainly through
hydroxymethyl group promoted hydrolysis process (Path B,
Scheme 2).
ACKNOWLEDGMENTS
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This research was supported by China Postdoctoral Science
Foundation (2013M540236), National Natural Science Foun-
dation of China (21306186), and the Chinese Government
“Thousand Talent” program funding.
Inspired by the above results, 4-(5-(hydroxymethyl)furan-2-
yl)but-3-en-2-one (HMFBE) was synthesized through con-
densation of 5-HMF with acetone. Cp*Ir-B was the most
effective catalyst for this reaction. Compared with the results of
5-HMF, the lower solubility of HMFBE in water may have
attributed to the decrease in catalytic reactivity, and nonane-
2,5,8-trione (2,5,8-NT) was obtained with 72% yield (Scheme
4).
REFERENCES
■
(1) Teong, S. P.; Yi, G.; Zhang, Y. Green Chem. 2014, 16, 2015−
2026.
(2) van Putten, R.-J.; van der Waal, J. C.; de Jong, E.; Rasrendra, C.
B.; Heeres, H. J.; de Vries, J. G. Chem. Rev. 2013, 113, 1499−1597.
(3) Zakrzewska, M. E.; Bogel-Łukasik, E.; Bogel-Łukasik, R. Chem.
Rev. 2011, 111, 397−417.
(4) Corma, A.; Iborra, S.; Velty, A. Chem. Rev. 2007, 107, 2411−
2502.
Scheme 4. Synthesis of 2,5,8-NT
(5) Jia, S.; Liu, K.; Xu, Z.; Yan, P.; Xu, W.; Liu, X.; Zhang, Z. C. Catal.
Today 2014, 234, 83−90.
(6) Zhao, H.; Holladay, J. E.; Brown, H.; Zhang, Z. C. Science 2007,
316, 1597−1600.
(7) Nikolla, E.; Roman
Catal. 2011, 1, 408−410.
(8) Roman-Leshkov, Y.; Chheda, J. N.; Dumesic, J. A. Science 2006,
́
-Leshkov, Y.; Moliner, M.; Davis, M. E. ACS
́
312, 1933−1937.
(9) Bozell, J. J.; Petersen, G. R. Green Chem. 2010, 12, 539−554.
(10) Nakagawa, Y.; Tamura, M.; Tomishige, K. ACS Catal. 2013, 3,
2655−2668.
In conclusion, we have demonstrated a highly efficient
homogeneous catalytic system for the hydrogenation/hydro-
lytic ring opening reaction of 5-HMF to produce biodiketones
HHD. High yield of HHD was achieved by using CP*Ir-A as
catalyst in water under mild conditions. This represents a
powerful addition to the suite of fundamental organic
transformations from biobased platform 5-HMF. The mecha-
nistic study based on the results of MS analysis and statistical
calculation not only allow us to rationalize our results but also
may broadly impact on the transformation of 5-HMF by
homogeneous catalysts. Further improvement of the catalyst
efficiency and developing a homogeneous catalytic process for
economic production of bioketones from 5-HMF are under-
way.
(11) Chen, J.; Lu, F.; Zhang, J.; Yu, W.; Wang, F.; Gao, J.; Xu, J.
ChemCatChem. 2013, 5, 2822−2826.
(12) Binder, J. B.; Raines, R. T. J. Am. Chem. Soc. 2009, 131, 1979−
1985.
(13) Roman-Leshkov, Y.; Barrett, C. J.; Liu, Z. Y.; Dumesic, J. A.
Nature 2007, 447, 982−985.
(14) Saha, B.; Bohn, C. M.; Abu-Omar, M. M. ChemSusChem 2014,
7, 3095−3101.
(15) Caretto, A.; Perosa, A. ACS Sustainable Chem. Eng. 2013, 1,
989−994.
́
(16) Chia, M.; Pagan-Torres, Y. J.; Hibbitts, D.; Tan, Q.; Pham, H.
N.; Datye, A. K.; Neurock, M.; Davis, R. J.; Dumesic, J. A. J. Am. Chem.
Soc. 2011, 133, 12675−12689.
́
(17) Buntara, T.; Noel, S.; Phua, P. H.; Melian-Cabrera, I.; de Vries,
ASSOCIATED CONTENT
J. G.; Heeres, H. J. Angew. Chem., Int. Ed. 2011, 50, 7083−7087.
(18) Zeng, C.; Seino, H.; Ren, J.; Hatanaka, K.; Yoshie, N.
Macromolecules 2013, 46, 1794−1802.
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S
* Supporting Information
The following file is available free of charge on the ACS
(19) Gupta, N. K.; Nishimura, S.; Takagaki, A.; Ebitani, K. Green
Chem. 2011, 13, 824−827.
(20) Julis, J.; Holscher, M.; Leitner, W. Green Chem. 2010, 12, 1634−
̈
Full experimental details and calculation details (PDF)
1639.
(21) Sutton, A. D.; Waldie, F. D.; Wu, R.; Schlaf, M.; ‘Pete’ Silks, L.
A., III; Gordon, J. C. Nat. Chem. 2013, 5, 428−432.
(22) Pupovac, K.; Palkovits, R. ChemSusChem 2013, 6, 2103−2110.
(23) Thananatthanachon, T.; Rauchfuss, T. B. ChemSusChem 2010,
3, 1139−1141.
(24) Deuss, P. J.; Barta, K.; de Vries, J. G. Catal. Sci. Technol. 2014, 4,
1174−1196.
AUTHOR INFORMATION
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Corresponding Author
Notes
The authors declare no competing financial interest.
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ACS Catal. 2015, 5, 788−792