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was irradiated using 25 W CFL for 5h to obtain the corresponding 3. (a) D. A. Nicewicz and D. W. C. MacMillan, Science, 2008, 322, 77–
DOI: 10.1039/C5CC03067F
alkyl halides in 60-70% yields. When adding external halogen source
such as NaBr and NaI for corresponding bromination and iodination,
the reactions could be completed within 3h in high yield (Table 3),
which are in accordance with the results obtained by Stephenson
and co-workers.13
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Table 3. Oxidative halogenation of alcohols to produce corresponding alkyl
halides under the optimized photo-catalytic conditions.a
R'
R'
Ru-POS
6a-e (alkyl bromide)
Br/I
7a-e (alkyl iodide)
+
CBr4 / CHI3
hν > 400 nm
CH3CN
R
R
OH
Entry
Alcohol
Product
Yield(%)
89 (6a)
92 (7a)
TOF (h-1
)
299
309
Ph
Ph
Br
I
1
Ph
OH
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Br
85 (6b)
82 (7b)
286
276
2
3
OH
I
Br
I
90 (6c)
91 (7c)
303
306
Me
Me
10
10
OH
Me
Me
10
Me
93 (6d)
91 (7d)
313
306
Me
Me
Br
Me
Me
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4
5
OH
I
88 (6e)
76 (7e)
296
255
Br
OH
I
a Alcohol (1 mmol), CBr4/CHI3 (2 mmol), NaBr/NaI (2 mmol), and Ru-POS (20 mg)
in 10 mL dry DMF under light irradiation for 3h or 5h
In summary, we have successfully incorporated [Ru(bpy)3]2+
within porous organosilica as a versatile heterogeneous photoredox
catalyst. The Ru-POS catalyst has been employed for three different
catalytic organic transformations. The catalyst has been exploited
both for reductive and oxidative quenching mediated catalytic
reactions to afford desired products in excellent yields. The newly
developed catalyst was found to be durable and reusable, and no
pre-activation was required to recover its catalytic activities. The
present work exhibits an approach for developing Ru-based
heterogeneous catalysts.
This work is supported by the National Research Foundation
(NRF), Prime Minister’s Office, Singapore under its NRF Fellowship
(NRF2009NRF-RF001-015), and Campus for Research Excellence and
Technological Enterprise (CREATE) Programme–Singapore Peking
University Research Centre for a Sustainable Low-Carbon Future, as
well as the NTU-A*Star Silicon Technologies Centre of Excellence
under program grant No. 112 351 0003. A.B. thanks DST, New Delhi
and S.M. thanks CSIR, New Delhi for the financial support.
9. X. Jia, L. Yu, C. Huo, Y. Wang, J. Liu and X. Wang, Tetrahedron
Lett., 2014, 55, 264–266.
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1463–1471.
11. M.-H. Larraufie, R. Pellet, L. Fensterbank, J.-P. Goddard, E.
Lacote, M. Malacria and C. Ollivier, Angew. Chem. Int. Ed., 2011,
50, 1–5,
Notes and references
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P. Yoon, M. A. Ischay and J. Du, Nature Chem., 2010, 2, 527–532;
(c) J. M. R. Narayanam and C. R. J. Stephenson, Chem. Soc. Rev.,
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2014, 343, 1239176.
12. A. Debache, W. Ghalem, R. Boulcina, A. Belfaitah, S. Rhouati and
B. Carboni, Tetrahedron Lett., 2009, 50, 5248–5250.
13. C. Dai, J. M. R. Narayanam and C. R. J. Stephenson, Nature
Chem., 2011, 3, 140-145.
2. (a) N. Hoffmann, Chem. Rev., 2008, 108, 1052–1103; (b) M.
Fagnoni, D. Dondi, D. Ravelli and A. Albini, Chem. Rev., 2007, 107,
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