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Chemical Science
Page 6 of 7
DOI: 10.1039/C7SC03768F
ARTICLE
Journal Name
Radicals in Chemistry, Biology and Materials, ed. C.
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Table 4 Catalytic methylation of Heteroarenes
2
3
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,
[a] Procedure: 1 (0.4 mmol, 1 equiv), 2,4-diphenylquinoline (0.008 mmol, 2 mol%,
2.3 mg), MeOH (0.8 mL), HCl (conc. In H2O, 2.0 mmol, 150 µL), c = 0.42 M, Ar
degas, irradiation with 1 X 410 nm LED for 24 h. Isolated yields are reported.
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,
,
7
4754. (h) C. A. Huff, R. D. Cohen, K. D. Dykstra, E. Streckfuss,
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G.-X. Li, C. A. Morales-Rivera, Y. Wang, F. Gao, G. He, P. Liu,
proceeded to give 2f in 90% yield. The facile photocatalytic
methylation described demonstrates the high potential for this
system to have broad applicability in the alkylation of a variety of
heteroarenes and will be investigated further.
G. Chen, Chem. Sci., 2016,
Tlahuext-Aca, G. Tavakoli, F. Glorius, ACS Catal., 2017,
7, 6407; (j) R. A. Garza-Sanchez, A.
7
,
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Conclusions
Molander, Chem. Sci. 2017, 8, 3512.
In summary, the photochemical alkylation of quinolines,
pyridines, and phenanthridine from alcohols and ethers was
described. Deuterium labelling studies showed the ability to
control the formation of CD3, CD2H, and CDH2 products,
indicating the reaction likely proceeds through an enamine
intermediate. We also reported the first photochemical
organic-mediated reduction of heteroarenes using simply
iPrOH and HCl. This study also provides mechanistic insights to
a complex reaction pathway and the possibility of a broadly
applicable catalytic system that will be disclosed in due
course.‡
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Acknowledgements
We thank the Natural Sciences and Engineering Research
Council (NSERC) for Discovery grants to L.B. and J.C.S. and the
University of Ottawa for a University Research Chair to L.B. and
Canada Research Chair Tier 1 to J.C.S. in support of this
research. Acknowledgement is also made to the donors of the
American Chemical Society Petroleum Research Fund for
support of this research. T.M. and S.P.P. thank NSERC for CGS-
D scholarships. M.M. thanks OGS for a Ph.D. scholarship.
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Notes and references
13 (a) J. J. Concepcion, M. K. Brennaman, J. R. Deyton, N. V.
Lebedeva, M. D. E. Forbes, J. M. Papanikolas, T. J. Meyer, J.
Am. Chem. Soc., 2007, 129, 6968. (b) J. Ravensbergen, C. L.
Brown, G. F. Moore, R. N. Frese, R. van Grondelle, D. Gust, T.
‡
Experimental procedures and analytical data for all new
compounds can be found in the Supporting Information.
1
(a) Radicals in Organic Synthesis, ed. P. Renaud and M. P.
Sibi, Wiley-VCH, Weinheim, 2001. (b) Encyclopedia of
6 | J. Name., 2012, 00, 1-3
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