10.1002/cctc.202000805
ChemCatChem
FULL PAPER
absorbed on CLM was 0.6 mg; thus, the palladium content of Pd/ CLM
(MeOH) was estimated to be 5% [(10.5 – 0.6)/210 × 100].
Maegawa, T. Takahashi, M. Yoshimura, H. Suzuka, Y. Monguchi, H.
Sajiki, Adv. Synth. Catal. 2009, 351, 2091–2095.
[7]
a) Y. Yabe, T. Yamada, S. Nagata, Y. Sawama, Y. Monguchi, H. Sajiki,
Adv. Synth. Catal. 2012, 354, 1264–1268; b) Y. Yabe, Y. Sawama, T.
Yamada, S. Nagata, Y. Monguchi, H. Sajiki, ChemCatChem 2013, 5,
2360–2366.
General procedure for chemoselective hydrogenation under batch
conditions (Table 2) A mixture of the substrate (250 μmol) and 5%
Pd/CLP or 5% Pd/CLM (5.3 mg, 2.5 μmol) in MeOH or EtOAc (1 mL) was
stirred at 25 or 50 °C using a test tube equipped with a H2 balloon. The
reaction was continuously monitored by thin-layer chromatography. After
a specific time, as indicated in Table 2, the mixture was filtered through a
membrane filter (pore size: 0.45 μm). The catalyst on the filter was
washed with ethyl acetate (5 mL × 3). The combined filtrates were
concentrated in vacuo to afford the corresponding analytically pure
product. If necessary, the product was further purified by silica-gel
column chromatography (hexane/EtOAc or hexane/diethyl ether). (1H and
13C spectra are presented in the Supporting Information).
[8]
[9]
Y. Monguchi, T. Marumoto, T. Ichikawa, Y. Miyake, Y. Nagae, M.
Yoshida, Y. Oumi, Y. Sawama, H. Sajiki, ChemCatChem 2015, 7,
2155–2160.
Y. Monguchi, F. Wakayama, S. Ueda, R. Ito, H. Takada, H. Inoue, A.
Nakamura, Y. Sawama, H. Sajiki, RSC Adv. 2017, 7, 1833–1840.
[10] a) L. Petridis, J.C. Smith, Nat. Rev. Chem. 2018, 2, 382–389; b) M.
Eibinger, J. Sattelkow, T. Ganner, H. Plank, B. Nidetzky, Nat. Commun.
2017, 8, 894; c) R. Brunecky, B. S. Donohoe, J. M. Yarbrough, A. Mittal,
B. R. Scott, H. Ding, L. E. Taylor II, J. F. Russell, D. Chung, J.
Westpheling, S. A. Teter, M. E. Himmel, Y. J. Bomble, Sci. Rep. 2017,
7, 9622; d) R. López-Mondéjar, D. Zühlke, D. Becher, K. Riedel, P.
Baldrian, Sci. Rep. 2016, 6, 25279; e) Angel T. Martínez, Science 2016,
352, 1050–1051; f) K. Kafle, H. Shin, C. M Lee, S. Park, S. H. Kim, Sci.
Rep. 2015, 5, 15102; g) M. E. Himmel, S.-Y. Ding, D. K. Johnson, W. S.
Adney, M. R. Nimlos, J. W. Brady, T. D. Foust, Science 2007, 315,
804–807; h) J. R. Rostrup-Nielsen, Science 2005, 308, 1421–1422.
[11] a) P. Langan, S. Gnanakaran, K. D. Rector, N. Pawley, D. T. Fox, D. W.
Cho, K. E. Hammel, Energy Environ. Sci. 2011, 4, 3820–3833; b) C.
Azar, K. Lindgren, E. Larson, K. Möllersten, Clim. Change 2006, 74,
47–79.
General procedure for hydrogenation under continuous-flow
conditions (Table 4) A solution of the substrate (250 μmol) in MeOH (10
mL, 0.05 M) was pumped into the catalyst-packed cartridge [5% Pd/CLM
(50.0 mg or 100 mg); φ 4.6 × 50 mm, stainless] at 0.1 mL/min using
hydrogen gas at a flow rate of 10 mL/min at 50 °C after introducing a flow
of MeOH and hydrogen gas into the cartridge under the same conditions
for ca. 5 min. The whole reaction mixture was collected and concentrated
in vacuo to give the corresponding hydrogenated product. If necessary,
the product was further purified by silica-gel column chromatography
(hexane/EtOAc).
[12] a) S. Tallarico, P. Costanzo, S. Bonacci, A. Macario, M. L. D. Gioia, M.
Nardi, A. Procopio, M. Oliverio, Sci. Rep. 2019, 9, 18858; b) C. Falter,
C. Zwikowics, D. Eggert, A. Blümke, M. Naumann, K. Wolff, D. Ellinger,
R. Reimer, C. A. Voigt, Sci. Rep. 2015, 5, 13722; c) M. B. Sticklen, Nat.
Rev. Genetics 2008, 9, 433–443.
Acknowledgements
[13] M. Wang, M. Liu, J. Lu, F. Wang, Nat. Commun. 2020, 11, 1083.
[14] D. W. Wakerley, M. F. Kuehnel, K. L. Orchard, K. H. Ly, T. E. Rosser, E.
Reisner, Nat. Energy 2017, 2, 17021.
We thank JNC Corporation for kindly gifting the cellulose
particles and cellulose monoliths and N. E. Chemcat Corporation
for the gift of palladium(II) acetate. We sincerely appreciate JNC
Corporation for providing joint research funding. This work is
partially based on results obtained from a project commissioned
by the New Energy and Industrial Technology Development
Organization (NEDO). We would like to thank Editage
[15] J. R. Regalbuto, Science 2009, 325, 822–824.
[16] Y. Wang, W. Deng, B. Wang, Q. Zhang, X. Wan, Z. Tang, Y. Wang, C.
Zhu, Z. Cao, G. Wang, H. Wan, Nat. Commun. 2013, 4, 2141.
[17] R. Palkovits, Angew. Chem. Int. Ed. 2010, 49, 4336–4338.
[18] B.-H. Cheng, B.-C. Huang, R. Zhang, Y.-L. Chen, S.-F. Jiang, Y. Lu, X.-
S. Zhang, H. Jiang, H.-Q. Yu, Sci. Adv. 2020, 6, eaay0748.
[19] a) D. Wang, Cellulose 2019, 26, 687–701; b) D. K. Patel, S. D. Dutta,
K.-T. Lim, RSC Adv. 2019, 9, 19143–19162; c) H. Voisin, L. Bergström,
P. Liu, A. P. Mathew, Nanomaterials 2017, 7, 57–75.
Keywords: Heterogeneous catalyst • Cellulose •
Chemoselective hydrogenation • Continuous-flow reaction •
Carbon-neutral support
[20] a) V. O. Okechukwu, V. Mavumengwana, I. A. Hümmelgen, M. A.
Mamo, ACS Omega 2019, 4, 8324–8333; b) X. Wang, Q. Zhang, C.
Nam, M. Hickner, M. Mahoney, M. E. Meyerhoff, Angew. Chem. Int. Ed.
2017, 56, 11826–11830.
[1]
[2]
[3]
a) S. Nishimura, Handbook of Heterogeneous Catalytic Hydrogenation
for Organic Synthesis, Wiley-Interscience, New York, 2001; b) van
Santen, R. A. Modern Heterogeneous Catalysis: An Introduction, Wiley,
Hoboken, 2017.
[21] a) S. Salimi, R. Sotudeh-Gharebagh, R. Zarghami, S. Y. Chan, K. H.
Yuen, ACS Sustainable Chem. Eng. 2019, 7, 15800–15827; b) G. F.
Picheth, C. L. Pirich, M. R. Sierakowski, M. A. Woehl, C. N. Sakakibara,
C. F. de Souza, A. A. Martin, R. de Silva, R. A. de Freitas, Int. J. Biol.
Macromolecules 2017, 104, 97–106; c) M. Jorfi, E. J. Foster, J. Appl.
Polym. Sci. 2015, 41719–41738.
a) L. Yin and J. Liebscher, Chem. Rev. 2007, 107, 133–173; b) M. J.
Climent, A. Corma and S. Iborra, Chem. Rev. 2011, 111, 1072–1133; c)
A. Molnár, Chem. Rev. 2011, 111, 2251–2320; d) I. Hussain, J.
Capricho, M. A. Yawer, Adv. Synth. Catal. 2016, 358, 3320–3349.
a) H. Sajiki, Y. Monguchi, in: Pharmaceutical Process Chemistry, (Eds.:
T. Shioiri, K. Izawa, T. Konoike), Wiley-VCH, Weinheim, 2010, pp. 77–
99; b) Y. Yabe, Y. Sawama, Y. Monguchi, H. Sajiki, Catal. Sci. Technol.
2014, 4, 260–271; c) Y. Monguchi, T. Ichikawa, H. Sajiki, Chem. Pharm.
Bull. 2017, 65, 2–9.
[22] a) A. Balea, E. Fuente, M. C. Monte, N. Merayo, C. Campano, C. Negro,
A. Blanco, Molecules 2020, 25, 526–545; b) C. I. Idumah, M. Zurina, J.
Ogbu, J. U. Ndem, E. C. Igba, Composite Interfaces 2020, 27, 1–72; c)
K. Uetani, H. Koga, M. Nogi, ACS Macro Lett. 2019, 8, 250–254.
[23] a) K. Fabičovicová, O. Malter, M. Lucas, P. Claus, Green Chem. 2014,
16, 3580–3588; b) J. Sun, W. G. Cheng, Z. F. Yang, J. Q. Wang, T. T.
Xu, J. Y. Xin, S. J. Zhang, Green Chem. 2014, 16, 3071–3078; c) S. P.
Satasia, P. N. Kalaria, D. K. Raval, RSC Adv. 2013, 3, 3184–3188.
[24] a) Y. Dong, Y. Lai, X. Wang, M. Gao, F. Xue, X. Chen, Y. Ma, Y. Wei,
Int. J. Biol. Macromol. 2019, 130, 778–785; b) D. Kale, G. Rashinkar, A.
Kumbhar, R. Salunkhe, React. Funct. Polym. 2017, 116, 9–16; c) A.
Pourjavadi, Z. Habibi, RSC Adv. 2015, 5, 99498–99501; d) J.-L. Huang,
D. G. Gray, C.-J. Li, Beilstein J. Org. Chem. 2013, 9, 1388–1396; e) Y.
Xu, M. Xue, J. Li, L. Zhang, Y. Cui, React. Kinet. Mech. Catal. 2010,
100, 347–353; f) K. R. Reddy, N. S. Kumar, P. S. Reddy, B. Sreedhar,
M. L. Kantam, J. Mol. Catal. Chem. 2006, 252, 12–16.
[4]
a) S. Mori, T. Ohkubo, T. Ikawa, A. Kume, T. Maegawa, Y. Monguchi, H.
Sajiki, J. Mol. Catal. A 2009, 307, 77–87; b) H. Sajiki, S. Mori, T.
Ohkubo, T. Ikawa, A. Kume, T. Maegawa, Y. Monguchi, Chem. Eur. J.
2008, 14, 5109–5111.
[5]
[6]
H. Sajiki, T. Ikawa, H. Yamada, K. Tsubouchi, K. Hirota, Tetrahedron
Lett. 2003, 44, 171–174.
a) T. Takahashi, M. Yoshimura, H. Suzuka, T. Maegawa, Y. Sawama,
Y. Monguchi, H. Sajiki, Tetrahedron 2012, 68, 8293–8299; b) T.
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