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Green Chemistry
Page 4 of 6
DOI: 10.1039/C8GC02387E
COMMUNICATION
Journal Name
2
(a) Top Value-Added Chemicals from Biomass Vol. I—Results of
Table 5 DODH-HG reaction of 1,2,6-hexanetriola
Screening for Potential Candidates from Sugars and Synthesis Gas
(eds. T. Werpy, G. Petersen), U. S. Department of Energy (DOE) by
the National Renewable Energy Laboratory, a DOE national
Laboratory, 2004; (b) P. J. Deuss, K. Barta, J. G. de Vries, Catal. Sci.
Technol., 2014, 4, 1174; (c) J. G. de Vries, Chem. Rec., 2016, 16,
2787.
E. Furimsky, Appl. Catal., A, 2000, 199, 147.
G. K. Cook, M. A. Andrews, J. Am. Chem. Soc.., 1996, 118, 9448.
(a) G. Chapman, K.M. Nicholas, Chem. Commun., 2013, 49, 8199; (b)
T.V. Gopaladasu, K.M. Nicholas, ACS Catal., 2016, 6, 1901
(a) L. Hills, R. Moyano, F. Montilla, A. Pastor, A. Galindo, E. Álvarez,
F. Marchetti, C. Pettinari, Eur. J. Inorg. Chem., 2013, 3352; (b) L.
Sandbrink, K. Beckerle, I. Meiners, R. Liffmann, K. Rahimi, J. Okuda,
R. Palkovits, ChemSusChem, 2017, 10, 1375.
THF
(mL)
0.5
2
Conv.
(%)
Yield (%)
Entry
Co-catal.
12
23
19
-
13
9
14
36
35
27
12
-
3
4
5
1
2
3
4
5
6
-
68
-
73
19
10
-
>99
>99
>99
>99
40
68(55)c
6
10
5% Pd/C
5% Pt/C
10% Ru/C
-
10
-
31
10
-
51
-
aReaction conditions: 1,2,6-hexanetriol (1.0 mmol), Re2O7 (0.05 mmol),
THF, 30 bar of H2, 165oC, 5h. bDetermined by 1H NMR spectroscopy
7
(a) S. Raju, M.-E. Moret, R. J. M. Klein Gebbink, ACS Catal., 2015, 5,
281; (b) J. R. Dethlefsen, P. Fristrup, ChemSusChem, 2015, 8, 767, (c)
S. Tin, J. G. de Vries, in Science of Synthesis: Catalytic Reduction in
Organic Synthesis, Ed. J. G. de Vries, Georg Thieme Verlag KG,
Stuttgart 2018, Vol 1, 229.
c
using dimethyl phthalate as internal standard. Isolated yields, 5 mmol
scale.
8
(a) S. Vkuturi, G. Chapman, I. Ahmad, K. M. Nicholas, Inorg. Chem.,
2010, 49, 4744; J. Yi, Shou Liu, M. M. Abu-Omar, ChemSusChem,
2012, 5, 1401; M. Shiramizu, F. D. Toste, Angew. Chem. Int. Ed.,
material was obtained with 0.75 mol% of 5% Pd/C. The
product was isolated in 55% yield after flash column
chromatography.
2012, 51, 8082; J. Davis, R. S. Srivastava, Tetrahedron Lett., 2014,
55, 4178; (b) E. Arceo, J. A. Ellman, R. G. Bergman, J. Am. Chem. Soc.,
2010, 132, 11408; (c) M. Shiramizu, F. D. Toste, Angew. Chem. Int.
Ed., 2013, 52, 12905; X. Li, D. Wu, T. Lu, G. Yi, H. Su, Y. Zhang,
Angew. Chem. Int. Ed., 2014, 53, 4200; (d) A. L. Denning, H. Dang, Z.
Conclusions
Liu, K. M. Nicholas, F. C. Jentoft, ChemCatChem, 2013,
Sandbrink, E. Klindtworth, H.-U. Islam, A. M. Beale, R. Palkovits, ACS
Catal., 2016, , 677.
(a) V. Schiavo, G. Descotes, J. Mentech, Bull. Soc. Chim. Fr., 1991,
128, 704; (b) F. liu, M. Audemar, K. De Oliveira Vigier, J.-M. Clacens,
F. De Campo, F. Jérôme, Green Chem., 2014, 16, 4110; (c) J. Ohyama,
A. Esaki, Y. Yamamoto, S. Arai, A. Satsuma, RSC Adv., 2013, 3, 1033;
(d) K. Gupta, D. Tyagi, A. D. Dwivedi, S. M. Mobin, S. K. Singh, Green
Chem., 2015, 17, 4618; (e) Z. Xu, P. Yan, W. Xu, X. Liu, Z. Xia, B.
5, 3567; L.
In summary, we developed a novel route for the conversion of
renewable triols into corresponding unsaturated alcohols.
Employing readily available and cheapest rhenium source
(Re2O7) under neat and ambient conditions at 165oC, we were
able to isolate the desired products in good to excellent yields.
We have shown that the activity and selectivity of the catalyst
depends on the position of a non-vicinal OH group in 5-HMF
based hexanetriols. In addition, we performed a one-pot
DODH-HG of 1,2,6 hexanetriols resulting in the formation of 1-
hexanol. The latter is a potential precursor for 1-hexene, an
important co-monomer for poly-ethylene which is currently
prepared by trimerisation of ethylene or Fisher-Tropsch on a
multi-ton scale. Further investigations on the isomerization
mechanism are currently on-going.
6
9
Chung, S. Jia, Z. C. Zhang, ACS Catal., 2015,
Xu, R. Zhu, M.-S. Cui, X.-L. Li, J. Deng, Y. Fu, ChemSusChem, 2016,
1209; (f) B. Wozniak, A. Spannenberg, Y. Li, S. Hinze, J. G. de Vries,
5, 788; (f) W.-P. Wu, Y.-J.
9
,
ChemSusChem, 2018, 11, 356, (g) B. Wozniak, Y. Li, S. Hinze, S. Tin, J.
G. de Vries, Eur. J. Org. Chem., 2018, 2009.
10 (a) R. Karinen, K. Vilonen, M. Niemela, ChemSusChem, 2011, 4, 1002; (b)
T. Ståhlberg, W. Fu, J. M. Woodley, A. Riisager, ChemSusChem, 2011, 4,
451; (c) R. J. van Putten, J. C. van der Waal, E. de Jong, C. B. Rasrendra,
H. J. Heeres, J. G. de Vries, Chem. Rev., 2013, 113, 1499; (d) J. G. de
Vries in Heterocyclic Chemistry in the 21st Century: A Tribute to Alan
Katritzky, Advances in Heterocyclic Chemistry Volume 121, ed. E.F.V.
Scriven, C.A. Ramsden, Academic Press (Elsevier), Cambridge, MA,
2017, 247.
11 a) T. Buntara, S. Noel, P. H. Phua, I. Melián-Cabrera, J. G. de Vries, H.
J. Heeres, Angew. Chem. Int. Ed., 2011, 50, 7083; Angew. Chem.,
2011, 123, 7221. b) T. Buntara, I. Melián-Cabrera, Q. Tan, José L.G.
Fierro, M. Neurock, Johannes G. de Vries, H. J. Heeres, Catal. Today
2013, 210, 106-116.
Conflicts of interest
There are no conflicts to declare
Acknowledgments
12 (a) Y. Amada, H. Watanabe, Y. Hirai, Y. Kajikawa, Y. Nakagawa, K.
We thank the Leibniz Foundation for financial support
(SAW-LIKAT-1 523)
Tomishige, ChemSusChem, 2012,
5
13 (a) R. Alamillo, M. Tucker, M. Chia, Y. Pagán-Torres, J. Dumesic,
5
M. Xian, H. Liu, Scientific Reports, 2015,
, 1991; (b) Y. Cao, W. Niu, J. Guo,
, 18149.
Green Chem., 2012, 14, 1413; (b) Y. Duan, J. Zhang, D. Li, D. Deng, L.-
F. Ma, Y. Yang, RSC Adv., 2017, 7, 26487
Notes and references
14 (a) J. Chen, F. Lu, J. Zhang, W. Yu, F. Wang, J. Gao, J. Xu, ChemCatChem,
2013, 5, 2822; (b) Y. Yang, Z. Du, J. Ma, F. Lu, J. Zhang, J. Xu
ChemSusChem, 2014, 7, 1352.
1
(a) A. J. Ragauskas, C. K. Williams, B. H. Davison, G. Britovsek, J.
Cairney, C. A. Eckert, W. J. Frederick Jr., J. P. Hallett, D. J. Leak, C. L.
Liotta, J. R. Mielenz, R. Murphy, R. Templer, T. Tschaplinski, Science,
2006, 311, 484; (b) P. N. R. Vennestøm, C. M. Omundsen, C. H.
Christensen, E. Taarning, Angew. Chem. Int. Ed., 2011, 50, 10502.
15 (a) W. Kuriyama, T. Matsumoto, Y. Ino, O. Ogata, WO 2011048727,
to Takasago International Corporation, Japan, 2011; (b) W.
Kuriyama, T. Matsumoto, O. Ogata, Y. Ino, K. Aoki, S. Tanaka, K.
Ishida, T. Kobayashi, N. Sayo, T. Saito, Org. Process Res. Dev., 2012,
4 | J. Name., 2012, 00, 1-3
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