Journal of the American Chemical Society
Page 4 of 6
This work was supported by the National Institutes of Health
(NIGMS) Award No. R01 GM120186 and an Eli Lilly Grantee
Award (D.A.N.).
nide to the corresponding radical. However it is unlikely that
this reaction proceeds through this pathway as it has been
shown that cyanide radical adds to arenes in an unselective
manner giving near statistical mixtures of the ortho, meta and
para-substituted products.40 Additionally, it has been shown
that the oxidation of cyanide in the presence of water quickly
generates cyanate anions.41 It is unlikely that cyanate anions
would act as reactive species to produce the desired benzo-
nitriles under in this system. Lastly, the observed ortho- para-
regioselectivity is consistent with prior work and can be best
explained by the location of partial charges on intermediate
5.25,27
1
2
3
4
5
6
7
8
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R
R
R
R
TMSCN
Me
2
5
7
H
3
NC
CN
–e–
+e–
Me
Me
O2
HOO
HOO
HOO
t-Bu
N
Ph
t-Bu
6 Mes-Acr•
O2
Mes-Acr+*
E1/2red* = +2.15 V
–e– +e–
Me
O2
hν
Me
Me
HOO
t-Bu
N
t-Bu
Ph
1 Mes-Acr+
Scheme 2: Possible mechanism for photoredox-mediated gen-
eration of benzonitriles.
In conclusion, we have developed a photoredox-catalyzed
system taking advantage of an acridinium photo-oxidant to
achieve direct C–H functionalization to furnish aromatic and
heteroaromatic nitriles. The conditions developed are mild and
proved to be compatible with sensitive or reactive functionali-
ties. The reaction also avoids undesired reactivity at the ben-
zylic positions of the substrates, allowing for exclusive aro-
matic ring C–H functionalization. Future studies are aimed at
elucidating the origins of the regioselectivity in more complex
substrates.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI:
Experimental procedures and supporting data
1H and 13C NMR spectra
AUTHOR INFORMATION
(26) Ohkubo, K.; Fujimoto, A.; Fukuzumi, S. J. Phys. Chem.
A 2013, 117, 10719–10725.
(27) Ohkubo, K.; Mizushima, K.; Iwata, R.; Fukuzumi, S.
Chem. Sci. 2011, 2, 715.
(28) Morofuji, T.; Shimizu, A.; Yoshida, J. J. Am. Chem.
Soc. 2014, 136, 4496–4499.
(29) Shu, Z.; Ji, W.; Wang, X.; Zhou, Y.; Zhang, Y.; Wang,
J. Angew. Chem. Int. Ed. 2014, 53, 2186–2189.
Corresponding Author
Funding Sources
No competing financial interests have been declared.
ACKNOWLEDGMENT
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