10.1002/anie.202010035
Angewandte Chemie International Edition
RESEARCH ARTICLE
was achieved with complete conversion (based on NMR
analysis).
Keywords: Catalysis Heterogenization • Bio-based Adipic Acid •
Aldaric Acids • Chemocatalytic Dehydroxylation • Rhenium
Catalyst
Reducing the catalyst (Re/C) before reaction and avoiding
contact with air (oxidizing atmosphere) have proven to be crucial
contributions to achieving higher yields of desired products.
Extensive characterization of the catalyst revealed that the most
active catalyst form (reduced one) has a lower oxidation state (0
or +3), while higher oxidation state (+6; oxidized form) is
associated with lower catalyst (dehydroxylation) activity and
higher solubility of the rhenium species in the liquid phase.
Reducing the catalyst increases its activity and extends its
stability for several consecutive experimental tests.
The study showed that the selective production of dimethyl
adipate (adipic acid precursor) does not require an external
source of hydrogen, normally used for hydrogenation of double
bonds produced by dehydroxylation. Methanol used as solvent
acts as a hydrogen donor. Dehydroxylated product with two
double bonds is thus selectively obtained at lower temperature
(120 °C), while dimethyl adipate is selectively obtained at higher
temperature (175 °C). At higher temperatures, the oxidation of
methanol to formaldehyde is more considerable, with hydrogen
being released (detected in the gas phase).
The mechanism of hydrogen generation from the solvent
was supported by extensive theoretical calculations (DFT). On
Re(0001), methanol readily gives off its hydroxylic hydrogen in a
low-barrier (0.25 eV) exothermic reaction (−0.70 eV), which
serves as the hydrogen source. In the second mildly
endothermic step, the ensuing CH3O* gives off the aliphatic
hydrogen and is ultimately oxidized to formaldehyde, which can
undergo further polymerization reactions. In the reaction with a
spectator OH* species, this oxidation to formaldehyde becomes
exothermic.
Esters of mucic acid undergo dehydroxylation by cleaving
the C-O bonds in fast and exothermic reactions, which explains
the fast formation of hexadienoates. Hydrogenation of the newly
formed double bonds is a slower endothermic reaction. Due to
stereochemistry of mucic acid, only two adjacent hydroxyl
groups can be cleaved off in a heterogeneous surface process
at a time.
[1]
[2]
[3]
H. Kawaguchi, T. Hasunuma, C. Ogino, A. Kondo, Curr. Opin.
Biotechnol. 2016, 42, 30–39.
J. Weisang, G. Szabo, J. Maurin, Dehydration Catalysts, Particularly
for the Dehydration of Diols, 1973, US3862964A.
C. Boucher-Jacobs, K. M. Nicholas, in Sel. Catal. Renew. Feed.
Chem. (Ed.: K.M. Nicholas), Springer International Publishing,
Cham, 2014, pp. 163–184.
[4]
[5]
[6]
[7]
E. Arceo, J. A. Ellman, R. G. Bergman, J. Am. Chem. Soc. 2010,
132, 11408–11409.
S. Raju, M.-E. Moret, R. J. M. Klein Gebbink, ACS Catal. 2015, 5,
281–300.
W. A. Herrmann, E. Herdtweck, M. Flöel, J. Kulpe, U. Küsthardt, J.
Okuda, Polyhedron 1987, 6, 1165–1182.
R. T. Larson, A. Samant, J. Chen, W. Lee, M. A. Bohn, D. M.
Ohlmann, S. J. Zuend, F. D. Toste, J. Am. Chem. Soc. 2017, 139,
14001–14004.
[8]
[9]
T. Yanagi, H. Suzuki, M. Oishi, Chem. Lett. 2013, 42, 1403–1405.
J. E. Ziegler, M. J. Zdilla, A. J. Evans, M. M. Abu-Omar, Inorg.
Chem. 2009, 48, 9998–10000.
[10]
M. Shiramizu, F. D. Toste, Angew. Chemie Int. Ed. 2012, 51, 8082–
8086.
[11]
[12]
[13]
[14]
J. Yi, S. Liu, M. M. Abu-Omar, ChemSusChem 2012, 5, 1401–1404.
J. O. Metzger, ChemCatChem 2013, 5, 680–682.
S. Dutta, ChemSusChem 2012, 5, 2125–2127.
E. V Makshina, M. Dusselier, W. Janssens, J. Degrève, P. A.
Jacobs, B. F. Sels, Chem. Soc. Rev. 2014, 43, 7917–7953.
K. P. Gable, E. C. Brown, J. Am. Chem. Soc. 2003, 125, 11018–
11026.
[15]
[16]
[17]
[18]
K. P. Gable, T. N. Phan, J. Am. Chem. Soc. 1994, 116, 833–839.
K. P. Gable, J. J. J. Juliette, J. Am. Chem. Soc. 1995, 117, 955–962.
K. P. Gable, B. Ross, in Feed. Futur., American Chemical Society,
2006, pp. 143–155.
[19]
[20]
S. Vkuturi, G. Chapman, I. Ahmad, K. M. Nicholas, Inorg. Chem.
2010, 49, 4744–4746.
M. Shiramizu, F. D. Toste, Angew. Chemie Int. Ed. 2013, 52,
12905–12909.
[21]
[22]
[23]
J. R. Dethlefsen, P. Fristrup, ChemSusChem 2015, 8, 767–775.
J. Gossett, R. Srivastava, Tetrahedron Lett. 2017, 58, 3760–3763.
A. L. Denning, H. Dang, Z. Liu, K. M. Nicholas, F. C. Jentoft,
ChemCatChem 2013, 5, 3567–3570.
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
T. J. Korstanje, E. F. de Waard, J. T. B. H. Jastrzebski, R. J. M.
Klein Gebbink, ACS Catal. 2012, 2, 2173–2181.
T. J. Korstanje, J. T. B. H. Jastrzebski, R. J. M. Klein Gebbink,
Chem. – A Eur. J. 2013, 19, 13224–13234.
N. Yoshinao, L. Sibao, T. Masazumi, T. Keiichi, ChemSusChem
n.d., 8, 1114–1132.
N. Ota, M. Tamura, Y. Nakagawa, K. Okumura, K. Tomishige,
Angew. Chemie Int. Ed. 2015, 54, 1897–1900.
S. Tazawa, N. Ota, M. Tamura, Y. Nakagawa, K. Okumura, K.
Tomishige, ACS Catal. 2016, 6, 6393–6397.
J. Shakeri, H. Hadadzadeh, H. Farrokhpour, M. Joshaghani, M. Weil,
J. Phys. Chem. A 2017, 121, 8688–8696.
Y. Xi, W. Yang, S. C. Ammal, J. Lauterbach, Y. Pagan-Torres, A.
Heyden, Catal. Sci. Technol. 2018, 8, 5750–5762.
G. Vilé, D. Albani, M. Nachtegaal, Z. Chen, D. Dontsova, M.
Antonietti, N. López, J. Pérez-Ramírez, Angew. Chemie Int. Ed.
2015, 54, 11265–11269.
It is noteworthy that the process is green, because a solid,
reusable catalyst is used, and the solvent (methanol or other
short-chain alcohols, also the internal source of hydrogen) can
also be recovered and reused. However, catalyst recycling is still
an area that needs improvements to achieve higher stability and,
consequently, life-cycle performance.
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
R. Lederkremer, C. Marino, Adv. Carbohydr. Chem. Biochem. 2004,
58, 199–306.
C. H. Hong, Y. G. Kim, N. SHIN, Synthetic Process of Adipic Acid,
2016, US9447012B2.
M. Asikainen, D. Thomas, A. Harlin, United States Pat. Appl. 2017,
DOI US Patent No. US20170137363A1.
X. Li, D. Wu, T. Lu, G. Yi, H. Su, Y. Zhang, Angew. Chemie Int. Ed.
2014, 53, 4200–4204.
N. Shin, S. Kwon, S. Moon, C. H. Hong, Y. G. Kim, Tetrahedron
2017, 73, 4758–4765.
A. V Kirilin, A. V Tokarev, H. Manyar, C. Hardacre, T. Salmi, J.-P.
Mikkola, D. Y. Murzin, Catal. Today 2014, 223, 97–107.
I. Khalil, G. Quintens, T. Junkers, M. Dusselier, Green Chem. 2020,
22, 1517–1541.
B. Hočevar, M. Grilc, B. Likozar, Catalysts 2019, 9, DOI
10.3390/catal9030286.
R. M. de Lederkremer, C. Marino, Academic Press, 2003, pp. 199–
306.
N. Ota, M. Tamura, Y. Nakagawa, K. Okumura, K. Tomishige, ACS
Catal. 2016, 6, 3213–3226.
S. Nishimura, Handbook of Heterogeneous Catalytic Hydrogenation
for Organic Synthesis, Wiley New York Etc, 2001.
P. N. Rylander, in Ullmann’s Encycl. Ind. Chem., 2000.
Acknowledgements
This work was funded by the Slovenian Research Agency
(ARRS) under core funding P2-0152 and postdoctoral project
Z2-9200. B. H. acknowledges funding from the Young
Researchers Programme from ARRS. Dr. Janez Kovač is
acknowledged for XPS measurement. Brett Pomeroy and
Florian Harth are acknowledged for English proofreading.
Ab initio calculations were performed on the computational
resources provided by the National Institute of Chemistry
(Ljubljana).
8
This article is protected by copyright. All rights reserved.