ACS Catalysis
Page 8 of 10
and we found that the existence of an electron-donating group on
alkoxyl atom can significantly promote the reaction, and vice versa.
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C
The existence of a β-H was found to be vital to a successful trans-
formation. To further understand the mechanistic details, a com-
putational study was performed via DFT calculations. The calcu-
lation results suggested a novel reaction pattern, in which the
C=O bond is believed to be cleaved rather than the Calkoxy-O bond
or the Cacyl-O bond. Moreover, based on our calculations, an oxo-
nium possessing OTf moiety is believed to be a critical intermedi-
ate in the transformation. To our delight, the existence of such an
oxonium was successfully confirmed by ESI-MS spectra. Our
theoretical studies also revealed that the hydrogenation actually
applies at a late stage and the lactone should be firstly transformed
into an unsaturated carboxylic acid. Different from the previous
study which emphasized solely on the effect of metal cation, our
study clearly pointed out the significant role that the anion plays.
Meanwhile, through a comparison with the Brønsted acid cata-
lyzed system, the study confirmed that the existence of OTf moie-
ty can significantly lower the barriers associated with the rear-
rangement and elimination processes. In addition, the anion effect
is directly related to the chemo-selectivity, thus providing insight-
ful information for the further catalyst design. At last, as a dessert
of this work, our strategy was also proved to be applicable to the
hydrogenolysis of renewable polymers (PHA), making it have
potential application in industry.
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AUTHOR INFORMATION
Corresponding Author
Author Contributions
†
(7) (a) Pritchard, J.; Filonenko, G. A.; Putten, R. v.; Emiel J. M.
Hensenab, E. J. M.; Pidko, E. A. Chem. Soc. Rev., 2015, 44,
3808-3833. (b) Werkmeister, S.; Junge, K.; Beller, M. Org. Pro-
cess Res. Dev. 2014, 18, 289-302. (c) Dub, P. A.; Ikariya, T. |
ACS Catal. 2012, 2, 1718-1741. (d) Cui, X.-J.; Li, Y.-H.; Topf,
C.; Junge, K.; Beller, M. Angew. Chem. Int. Ed. 2015, 54,
R. Zhu and J. Jiang contributed equally.
Notes
The authors declare no competing financial interests
ASSOCIATED CONTENT
Supporting Information.
1
0596-10599.
(8) (a) Bond, J. Q.; Alonso, D. M.; Wang, D.; West, R. M.; Dumesic,
J. A. Science 2010, 327, 1110-1114. (b) Qi, L.; Mui, Y. F.; Lo, S.
W.; Lui, M. Y.; Akien, G. R.; Horváth, I. T. ACS Catal. 2014, 4,
1470-1477.
X-ray crystallographic data for 19489-18-0 (CIF)
X-ray crystallographic data for 19489-16-8 (CIF)
Full experimental details, experimental procedures, products
(9) (a) Werpy, T.; Petersen, G. Top value added chemicals from
1
13
characterization data including H and C NMR spectra, detailed
mechanistic data and data of X-ray crystallographic structures
(PDF)
biomass. In Re-sults of Screening for Potential Candidates from
Sugars
http://www.nrel.gov/docs/fy04osti/35523.pdf (US DOE, 2004).
b) Yan, K.; Yang, Y.-Y.; Chai, J.-J.; Lu, Y.-R. Appl. Catal.
and
Synthe-sis
Gas
Vol.
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45-48,
(
ACKNOWLEDGMENT
B 2015, 179, 292-304. (c) Tang, X.; Zeng, X.-H.; Zheng Li, Z.;
Hu, L.; Sun, Y.; Liu, S.-J.; Tingzhou Lei, T.-Z.; Lin, L. Renewa-
ble Sustainable Energy Rev. 2014, 40, 608-620. (d) Yang, Z.; Fu,
Y.; Guo, Q.-X. Chin. J. Org. Chem. 2015, 35, 273-283. (e)
Horváth, I. T.; Mehdi, H.; Fábos, V.; Boda, L.; Mika, L. T.
Green Chem. 2008, 10, 238-242.
This work was supported by NSFC (21572212, 21402181,
21325208), CAS (XDB20000000, YZ201563), FRFCU and
PCSIRT. The supercomputer center in the USTC is also acknowl-
edged for providing the computational resources.
(10) (a) Lange, J.-P.; Price, R.; Ayoub, P. M.; Louis, J.; Petrus, L.;
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