10.1002/anie.201904159
Angewandte Chemie International Edition
COMMUNICATION
(15c), which is a monomer for the synthesis of heat-resistant
Acknowledgements
polymer,[1m] was obtained in quantitative yield (Scheme 3-(d)).
This work was supported in part by a Grant-in-Aid for Scientific
Research from JSPS, the University of Tokyo, and MEXT (Japan),
JST. We thank Mr. Noriaki Kuramitsu (University of Tokyo) for
STEM and EDS analyses.
O
Cl
/DMF (1/19),
(a)
OAc
H2 (3.33 mL/min)
5.0 eq., 0.053 mL/min
H2
φ 3 mm x 5 m
in sonicator
8a
7a
in DMF, 0.075 M
0.10 mL/min
12a
OAc
10 (864 mg), 30 ºC
pyridine/DMF (1/9),
DMAP (20 mol%)
0.03 mL/min
Keywords: continuous-flow reaction • quinone • hydrogenation •
83%
(b)
metal nanoparticle catalyst • hydroquinone
OH
O
OTf
H2 (3.33 mL/min)
H2
φ 3 mm x 5 m
in sonicator
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7c
8c OH
O
10 (745 mg), 30 ºC
Tf2O/DCM (0.35 M),
5.0 eq., 0.11 mL/min
13c
OTf
in pyridine, 0.075 M
0.10 mL/min
89%
(c)
OH
O
OBz
H2 (3.33 mL/min)
H2
φ 3 mm x 1 m
at 35 ºC bath
7c
8c OH
O
10 (745 mg), 30 ºC
BzCl/DCM (0.35 M),
5.0 eq., 0.022 mL/min
14c
OBz
in pyridine, 0.075 M
DMAP (20 mol%)
0.10 mL/min
99%
O
OH
(d)
O
O
O
H2 (3.33 mL/min)
H2
φ 3 mm x 1 m
at 35 ºC bath
7c
8c OH
O O
O
10 (745 mg), 30 ºC
15c
>99%
in pyridine, 0.075 M
0.10 mL/min
O
/DCM (1/4),
DMAP (20 mol%)
5.0 eq., 0.028 mL/min
O
Scheme 3. Scope of derivatization of hydroquinones generated in situ.
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In summary, we have developed Pt-Au bimetallic nanoparticle
catalysts for selective hydrogenation of quinone to hydroquinone.
Catalysts immobilized on dimethyl polysilane (Pt-Au/(DMPSi-
Al2O3) (10)) showed great catalytic performance for
hydrogenation of anthraquinone derivatives under continuous-
flow conditions. Overreduced products and side products, which
easily poisoned hydrogenation catalysts, were not formed in this
flow process. Various direct derivatizations of quinones;
methylation, acetylation, trifluoromethanesulfonylation, and
benzoylation were successfully performed under sequential
continuous-flow conditions and the desired products were
obtained in good to excellent yields. Especially, air-sensitive
[4]
[5]
hydroquinones,
such
as
anthrahydroquinones
and
naphthohydroquinones, could be generated under closed
sequential flow conditions and they were derivatized without
decomposition. It is noted that the first flow hydrogenation was
very robust and catalytic performance was not diminished over
several weeks. In addition, various solvent systems including
additives could be employed in the first flow hydrogenation step
depending on the requirement from the second derivatization
reactions. The truly robust nature of both catalyst 10 and the
newly developed sequential flow system was confirmed. This flow
hydrogenation system will open efficient synthetic routes toward
various molecules containing polyaromatic skeletons, such as
anthracene and naphthalene, that can be seen in various
biologically active compounds and organic electronic materials.
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