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Catalysis Science & Technology
Page 4 of 6
DOI: 10.1039/C6CY00899B
COMMUNICATION
the University
Journal Name
Lett., 2009, 133, 63–69; (d) C. Hubert, A. Denicourt-Nowicki,
A. Roucoux, D. Landy, B. Leger, G. Crowyn and E. Monflier,
Chem. Commun., 2009, 1228–1230; Rh: (e) C. Hubert, A.
Denicourt-Nowicki, J.-P. Guégan and A. Roucoux, Dalton
Trans., 2009, 38, 7356–7358; (f) C. Hubert, A. Denicourt-
of
Cambridge
data
repository
(see
https://www.repository.cam.ac.uk/handle/xxxx/yyyyyy).
Notes and references
Nowicki, P. Beaunier and A. Roucoux, Green Chem., 2010, 12
,
1167–1170; (g) E. G. Bilé, R. Sassine, A. Denicourt-Nowicki, F.
Launay and A. Roucoux, Dalton Trans., 2011, 40, 6524–6531.
11 During the review process for this manuscript, arene
hydrogenation of benzyl ethers by Ru/carbon-nitrogen matrix
was reported: X. Cui, A.-E. Surkus, K. Junge, C. Topf, J. Radnik,
1
M. J. Palframan and A. F. Parsons, Product class 4: Five
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(a) S. Nishimura, Hydrogenation of Aromatic Compounds, in
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Selective arene hydrogenation remains a major issue in
current synthetic chemistry: (a) I. S. Park, M. S. Kwon, K. Y.
2
C. Kreyenschulte and M. Beller, Nat. Commun., 2016,
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Wheatley, S. Saito and H. Naka, RSC Adv., 2015, 5, 12152–
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14 Chitin is the second most abundant polysaccharide in nature:
Chitin: Formation and Diagenesis, ed. N. S. Gupta, Springer,
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16 2a can also be a (co)monomer for preparing epoxide resins.
17 (a) Ref 9c: 1a (0.5 mmol), Rh/CNF-T (10 mg, 0.2 wt % Rh, 0.04
mol % Rh), H2 (1 MPa), n-hexane (1 mL), rt, 12 h; 2a, > 99%
yield; (b) Ref 9d: 1a (1 mmol), Ru/HPS-NR3Cl (0.3 mol % Ru),
H2 (3 MPa), H2O (1 mL), 30 °C, 24 h; 2a, 96% yield.
18 Ru/C and Rh/C are excellent, general catalysts for arene
hydrogenation: T. Maegawa, A. Akashi, K. Yaguchi, Y. Iwasaki,
M. Shigetsura, Y. Monguchi and H. Sajiki, Chem. Eur. J., 2009,
15, 6953–6963.
19 The origin of high selectivity in the hydrogenation of 1a with
Ru/chitin remains unclear. Coordination of hydroxyl groups in
the chitin to the Ru metal does not seem to suppress
catalytic activity for side reactions; selectivity in the
hydrogenation with Rh/Al2O3, Ru/C or Rh/C was not
significantly altered by adding ethylene glycol (Table S2,
entries 1–3). Meanwhile, coordination of acetamide groups
to the Ru metal may partly account for the high selectivity of
Ru/chitin; addition of N-acetylethanolamine increased
selectivity for arene hydrogenation with Rh/C (Table S2, entry
5).
Roucoux, ACS Sustainable Chem. Eng., 2016,
(f) M. M. Stalzer, C. P. Nichloas, A. Bhattacharyya, A. Motta,
4, 1834–1839;
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8
9
20 T. L. Amyes, J. P. Richard and M. Novak, J. Am. Chem. Soc.,
1992, 114, 8032–8041.
(a) Y. Motoyama, M. Takasaki, K. Higashi, S.-H. Yoon, I.
Mochida and H. Nagashima, Chem. Lett., 2006, 35, 876–877
(CNF-P = platelet carbon nanofibers); (b) M. Takasaki, Y.
Motoyama, K. Higashi, S.-H. Yoon, I. Mochida and H.
21 The reason for a small amount of racemization in Table 2,
entries 2 and 9 is not entirely clear, but we assume it to
result from dehydrogenation of alcohol or amine•HCl
followed by hydrogenation of the resulting ketones and
imminium salts. This view is based on the following
observations: (1) In Table 2, entry 4, ketone 5e formed in 7%
yield; (2) Hydrogenation of acetophenone with Ru/chitin
under the standard conditions yielded cyclohexyl methyl
ketone (20%), 1c (27%) and 2c (52%).
Nagashima, Chem. Asian J., 2007,
2, 1524–1533; (c) Y.
Motoyama, M. Takasaki, S.-H. Yoon, I. Mochida and H.
Nagashima, Org. Lett., 2009, 11, 5042–5045 (CNF-T = tubular
carbon nanofibers); (d) L. Gao, K. Kojima and H. Nagashima,
Tetrahedron, 2015, 71, 6414–6423 (HPS-NR3Cl = ammonium
salts of hyperbranched polystyrene).
22 Hydrogenation of dibenzyl ether (100 °C, 6 h, 91% conv.) gave
a mixture of bis(cyclohexylmethyl) ether (27%), benzyl
cyclohexylmethyl ether (38%), 2b (7%) and other
10 For examples of Ru or Rh nanoparticle catalysts for arene
hydrogenation in water, see: Ru: (a) A. Nowicki, Y. Zhang, B.
Léger, J.-P. Rolland, H. Bricout, E. Monflier and A. Roucoux,
Chem. Commun., 2006, 296–298; (b) A. Nowicki, V. Le
Boulaire and A. Roucoux, Adv. Synth. Catal., 2007, 349, 2326–
2330; (c) L. Song, X. Li, H. Wang, H. Wu and P. Wu, Catal.
unidentified products. Hydrogenation of dibenzylamine•HCl
mixture of
(100 °C,
5
h,
>
99% conv.) gave
a
bis(cyclohexylmethyl)amine•HCl (21%) and 2i•HCl (74%).
4 | J. Name., 2016, 00, 1-3
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