ACS Catalysis
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such as ketone, ester, or amide groups were
selectively hydrogenated under the aqueous flow
conditions (40–100 °C, 30 bar) to give the
corresponding primary alcohols in up to 99% yield,
leaving the other substituents intact. Moreover
long-term continuous-flow hydrogenation of
benzaldehyde was realized. The total turnover
number reached 997 during eight days. This flow
system therefore provides an efficient and practical
method for the selective catalytic hydrogenation of
aldehydes bearing reducible functional groups,
such as ketone, ester, or amide groups.
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ASSOCIATED CONTENT
Supporting Information
Analytical data for products 2 and 4, (1H, and 13C{1H} NMR
spectra, MS data). This material is available free of charge
AUTHOR INFORMATION
(6) Mäki-Arvela, P.; Hájek, J.; Salmi, T.; Murzin, D. Y. App.
Catal. A 2005, 292, 1–49.
Corresponding Author
(7) For example, the SciFinder search for the conversion of 4-
acetoxybenzaldehyde to 4-acetoxybenzylalcohol showed only
one example for the chemoselective heterogeneous catalytic
hydrogenation using molecular hydrogen; Kotha, S. S.; Sharma,
N.; Sekar, G. Adv. Synth. Catal. 2016, 358, 1694–1698.
(8) Recent typical reviews for flow chemistry, see; (a)
Kobayashi S. Chem. Asian J. 2016, 11, 425–436. (b) Mallia, C.
J.; Baxendale, I. R. Org. Process Res. Dev. 2016, 20, 327–360.
(c) Gutmann, B.; Cantillo, D.; Kappe, C. O. Angew. Chem. Int.
Ed. 2015, 54, 6688–6728. (d) Munirathinam, R.; Huskens, J.;
Verboom, W. Adv. Synth. Catal. 2015, 357, 1093–1123. (e)
Ricciardi, R.; Huskens, J.; Verboom, W. ChemSusChem 2015,
8, 2586–2605. (f) Baumann, M.; Baxendale, I. R. Beilstein J.
Org. Chem. 2015, 11, 1194–1219. (g) Vaccaro, L.; Lanari, D.;
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3704. (h) Newman, S. G.; Jensen, K. F. Green Chem. 2013, 15,
1456–1472.
(9) Reviews for flow hydrogenation, see; (a) Cossar, P. J.;
Hizartzidis, L.; Simone, M. I.; McCluskey, A.; Gordon, C. P. Org.
Biomol. Chem. 2015, 13, 7119–7130. (b) Irfan, M.; Glasnov, T.
N.; Kappe, C. O. ChemSusChem., 2011, 4, 300–316 and
references therein. Typical recent examples for the catalytic
flow hydrogenation: (c) Cantillo, D.; Wolf, B.; Goetz, R.; Kappe,
C. O. Org. Process Res. Dev. 2017, 21, 125–132. (d) Furuta, A.;
Hirobe, Y.; Fukuyama, T.; Ryu, I.; Manabe, Y.; Fukase, K. Eur.
J. Org. Chem. 2017, 1365–1368. (e) Pélisson, C.-H.; Nakanishi,
T.; Zhu, Y.; Morisato, K.; Kamei, T.; Maeno, A.; Kaji, H.;
Muroyama, S.; Tafu, M.; Kanamori, K. Shimada, T.; Nakanishi,
K. ACS Appl. Mater. Interfaces 2017, 9, 406–412. (f) Ichire, O.;
Jan, P.; Parfenov, G.; Dounay, A. B. Tetrahedron Lett. 2017,
58, 582–585. (g) Paun, C.; Slowik, G.; Lewin, E.; Sá, J. RSC
Adv. 2016, 6, 87564–87568. (h) Rathi, A. K.; Gawande, M. B.;
Ranc, V.; Pechousek, J.; Petr, M.; Cepe, K.; Varma, R. S.; Zboril,
R. Catal. Sci. Technol. 2016, 6, 152–160. (i) Hattori, T.; Ida, T.;
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Chem. 2015, 2492–2497. (j) Kobayashi, S.; Okumura, M.;
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* uo@ims.ac.jp
ORCID
Takao Osako: 0000-0003-0621-4272
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
This work was supported by the JST ACCEL (Development
of Key Chemical Processes of Extremely High Efficiency
with Super-Performance Heterogeneous Catalysts), JST
CREST (Creation of Innovative Functions of Intelligent
Materials on the Basis of Element Strategy). We appreciate
funding from the JSPS KAKENHI [Grant-in-Aid for
Scientific Research on Innovative Area no. 2707; Grant-in-
Aid for Young Scientists (B) no. 26810099; Grant-in-Aid for
Scientific Research (C) no. 15F15039].
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