ChemComm
Communication
attempted the oxidative C–H/C–H cross-coupling of coumarins
with arenes at room temperature. Pleasantly, the reaction
occurred in a highly regioselective manner and the 3-arylated
coumarins were obtained in 74–79% yields (Table 2, 6a–6c).
Arylated quinones are found to have a wide range of applications
Y. Huang, Angew. Chem., Int. Ed., 2012, 51, 7242; (d) P. Zhao, R. Niu,
F. Wang, K. Han and X. Li, Org. Lett., 2012, 14, 4166; (e) L. Zheng and
J. Wang, Chem. – Eur. J., 2012, 18, 9699; ( f ) Y. Wang, C. Li, Y. Li, F. Yin
and X.-S. Wang, Adv. Synth. Catal., 2013, 355, 1724; (g) D. Zhao,
C. Nimphius, M. Lindale and F. Glorius, Org. Lett., 2013, 15, 4504;
(
h) T. Zhang, L. Wu and X. Li, Org. Lett., 2013, 15, 6294; (i) Y. Dong and
G. Liu, Chem. Commun., 2013, 49, 8066; ( j) C. Suzuki, K. Morimoto,
K. Hirano, T. Satoh and M. Miura, Adv. Synth. Catal., 2014, 356, 1521;
(k) K. Nobushige, K. Hirano, T. Satoh and M. Miura, Org. Lett., 2014,
16, 1188; (l) N.-J. Wang, S.-T. Mei, L. Shuai, Y. Yuan and Y. Wei, Org.
Lett., 2014, 16, 3040; (m) K. Parthasarathy and C. Bolm, Chem. – Eur. J.,
18
in the dye industry by virtue of their significant coloring properties.
Consequently, a variety of methods have been established for the
19
synthesis of such molecules. Our group recently reported a highly
efficient approach to synthesize arylquinones through the oxidation
of hydroquinones and subsequent palladium-catalyzed oxidative
2014, 20, 4896.
5 For selected examples of Ru-catalyzed olefination of arenes, see:
(a) H. Weissman, X. Song and D. Milstein, J. Am. Chem. Soc., 2001,
20
C–H/C–H cross-coupling of the resulting quinones with arenes.
123, 337; (b) L. Ackermann, L. Wang, R. Wolfram and A. V. Lygin,
However, this reaction suffered from the employment of stoichio-
metric amounts of Ag CO as the oxidant and a high reaction
Org. Lett., 2012, 14, 728; (c) B. Li, J. Ma, N. Wang, H. Feng, S. Xu and
B. Wang, Org. Lett., 2012, 14, 736; (d) K. Padala and M. Jeganmohan,
Org. Lett., 2012, 14, 1134; (e) K. Graczyk, W. Ma and L. Ackermann,
Org. Lett., 2012, 14, 4110; ( f ) K. Padala, S. Pimparkar, P. Madasamy
and M. Jeganmohan, Chem. Commun., 2012, 48, 7140; (g) J. Li,
C. Kornhaaß and L. Ackermann, Chem. Commun., 2012, 48, 11343;
2
3
2 4 2 2 8
temperature (140 1C). Pleasantly, by using the [Pd(TFA) ]/(NH ) S O
catalytic system described herein, the coupling of quinones with
arenes proceeded smoothly at room temperature to afford the
desired arylquinones 7 in modest to excellent yields (Table 2,
(
(
h) W. Ma and L. Ackermann, Chem. – Eur. J., 2013, 19, 13925;
i) H. Li, X. Xie and L. Wang, Chem. Commun., 2014, 50, 4218.
7a–7e). Besides electron-donating groups, electron-deficient arenes
6
(a) M. D. K. Boele, G. P. F. van Strijdonck, A. H. M. de Vries, P. C. J. Kamer,
J. G. de Vries and P. W. N. M. van Leeuwen, J. Am. Chem. Soc., 2002,
such as 1,2-dichlorobenzene were also tolerated (Table 2, 7e).
1
24, 1586; (b) T. Nishikata and B. H. Lipshutz, Org. Lett., 2010, 12, 1972;
(c) B. S. Kim, C. Jang, D. J. Lee and S. W. Youn, Chem. – Asian J., 2010,
, 2336; (d) X. Liu and K. K. Hii, J. Org. Chem., 2011, 76, 8022;
A controlled experiment of 1,4-naphthoquinone with benzene
2
1
indicated that no reaction occurred in the absence of Pd(OAc)2.
In conclusion, by employing highly electrophilic [Pd(TFA) ] as the
catalyst and the inexpensive and environmentally friendly
NH as the oxidant, we have successfully realized the oxidative
5
2
(e) B. Schmidt and N. Elizarov, Chem. Commun., 2012, 48, 4350.
P. Gandeepan and C.-H. Cheng, J. Am. Chem. Soc., 2012, 134, 5738.
X. Huang, J. Huang, C. Du, X. Zhang, F. Song and J. You, Angew.
Chem., Int. Ed., 2013, 52, 12970.
7
8
(
4 2 2 8
) S O
C–H/C–H cross-coupling of (hetero)arenes with alkenes under air at
room temperature. More importantly, the current methodology can
also be applied to the coupling reactions between simple arenes and
other important alkene-related functional molecules such as
coumarins and quinones. These transformations are operationally
simple and do not require the exclusion of air or moisture.
We acknowledge the financial support from the National Basic
Research Program of China (973 Program, 2011CB808600), and the
National NSF of China (21202105, 21025205, 21272160, 21321061,
J1310008 and J1103315).
9 B. Liu, Y. Fan, Y. Gao, C. Sun, C. Xu and J. Zhu, J. Am. Chem. Soc.,
013, 135, 468.
2
1
0 (a) C. Jia, D. Piao, J. Oyamada, W. Lu, T. Kitamura and Y. Fujiwara,
Science, 2000, 287, 1992; (b) C. Jia, W. Lu, J. Oyamada, T. Kitamura,
K. Matsuda, M. Irie and Y. Fujiwara, J. Am. Chem. Soc., 2000, 122, 7252.
1 F. Yang, F. Song, W. Li, J. Lan and J. You, RSC Adv., 2013, 3, 9649.
2 R. Li, L. Jiang and W. Lu, Organometallics, 2006, 25, 5973.
3 Y. Taniguchi, Y. Yamaoka, K. Nakata, K. Takaki and Y. Fujiwara,
Chem. Lett., 1995, 345.
1
1
1
1
1
4 P. Fang, M. Li and H. Ge, J. Am. Chem. Soc., 2010, 132, 11898.
5 (a) Y. Huang, F. Song, Z. Wang, P. Xi, N. Wu, Z. Wang, J. Lan and
J. You, Chem. Commun., 2012, 48, 2864; (b) L.-Q. Zhang, S. Yang,
X. Huang, J. You and F. Song, Chem. Commun., 2013, 49, 8830.
6 For selected examples, see: (a) M. Khoobi, M. Alipour, S. Zarei,
F. Jafarpour and A. Shafiee, Chem. Commun., 2012, 48, 2985;
1
Notes and references
(
b) Y. Li, Z. Qi, H. Wang, X. Fu and C. Duan, J. Org. Chem., 2012,
1
2
I. Moritani and Y. Fujiwara, Tetrahedron Lett., 1967, 8, 1119.
(a) J. L. Bras and J. Muzart, Chem. Rev., 2011, 111, 1170; (b) C. S. Yeung
and V. M. Dong, Chem. Rev., 2011, 111, 1215; (c) C. Liu, H. Zhang,
77, 2053; (c) M. Min and S. Hong, Chem. Commun., 2012, 48, 9613;
(d) F. Jafarpour, H. Hazrati, N. Mohasselyazdi, M. Khoobi and
A. Shafiee, Chem. Commun., 2013, 49, 10935.
W. Shi and A. Lei, Chem. Rev., 2011, 111, 1780; (d) S. I. Kozhushkov 17 (a) L. M. Kabeya, A. A. de Marchi, A. Kanashiro, N. P. Lopes, C. H. T. P. da
and L. Ackermann, Chem. Sci., 2013, 4, 886; (e) Y. Wu, J. Wang, F. Mao
and F. Y. Kwong, Chem. – Asian J., 2014, 9, 26.
For selected examples of Pd-catalyzed olefination of simple arenes, see:
Silva, M. T. Pupo and Y. M. Lucisano-Valima, Bioorg. Med. Chem., 2007,
15, 1516; (b) L. You, R. An, X. Wang and Y. Li, Bioorg. Med. Chem. Lett.,
2010, 20, 7426; (c) P. Anand, B. Singh and N. Singh, Bioorg. Med. Chem.
Lett., 2012, 20, 1175; (d) D. Olmedo, R. Sancho, L. M. Bedoya, J. L. L ´o pez-
P ´e rez, E. del Olmo, E. Mu n˜ oz, J. Alcam ´ı , M. P. Gupta and A. S. Feliciano,
Molecules, 2012, 17, 9245; (e) M. J. Matos, S. Vazquez-Rodriguez,
L. Santana, E. Uriarte, C. Fuentes-Edfuf, Y. Santos and A. Mu n˜ oz-Crego,
Molecules, 2013, 18, 1394.
3
(
(
a) C. Jia, W. Lu, T. Kitamura and Y. Fujiwara, Org. Lett., 1999, 1, 2097;
b) T. Matsumoto and H. Yoshida, Chem. Lett., 2000, 1064; (c) M. Dams,
D. E. De. Vos, S. Celen and P. A. Jacobs, Angew. Chem., Int. Ed., 2003,
2, 3512; (d) T. Yokota, M. Tani, S. Sakaguchi and Y. Ishii, J. Am. Chem.
Soc., 2003, 125, 1476; (e) Y.-H. Zhang, B.-F. Shi and J.-Q. Yu, J. Am. Chem.
4
Soc., 2009, 131, 5072; ( f ) A. Kubota, M. H. Emmert and M. S. Sanford, 18 T. Bechtold, in Handbook of Natural Colorants, ed. T. Bechtold and
Org. Lett., 2012, 14, 1760; (g) B. P. Babu, X. Meng and J.-E. B ¨a ckvall,
R. Mussak, Wiley, New York, 2009, p. 151.
Chem. – Eur. J., 2013, 19, 4140; for selected recent examples of Pd-catalyzed 19 For selected examples, see: (a) H.-B. Zhang, L. Liu, Y.-J. Chen, D. Wang
olefination of arenes with directing groups, see: (h) A. Garc ´ı a-Rubia,
B. Urones, R. G. Array ´a s and J. C. Carretero, Angew. Chem., Int. Ed., 2011,
and C.-J. Li, Adv. Synth. Catal., 2006, 348, 229; (b) M. R. Heinrich,
Chem. – Eur. J., 2009, 15, 820; (c) X. Gan, W. Jiang, W. Wang and
L. Hu, Org. Lett., 2009, 11, 589; (d) M. T. Molina, C. Navarro, A. Moreno
and A. G. Cs ´a k ¨y , Org. Lett., 2009, 11, 4938; (e) O. M. Demchuk and
K. M. Pietrusiewicz, Synlett, 2009, 1149; ( f ) Y. Fujiwara, V. Domingo,
I. B. Seiple, R. Gianatassio, M. D. Bel and P. S. Baran, J. Am. Chem. Soc.,
2011, 133, 3292; (g) J. Wang, S. Wang, G. Wang, J. Zhang and X.-Q. Yu,
Chem. Commun., 2012, 48, 11769.
5
0, 10927; (i) C. Huang, B. Chattopadhyay and V. Gevorgyan, J. Am. Chem.
Soc., 2011, 133, 12406; ( j) R. D. Baxter, D. Sale, K. M. Engle, J.-Q. Yu and
D. G. Blackmond, J. Am. Chem. Soc., 2012, 134, 4600; (k) X. Cong, J. You,
G. Gao and J. Lan, Chem. Commun., 2013, 49, 662; (l) H.-L. Wang, R.-B. Hu,
H. Zhang, A.-X. Zhou and S.-D. Yang, Org. Lett., 2013, 15, 5302.
4
For selected recent examples of Rh-catalyzed olefination of arenes, see:
(
5
a) F. W. Patureau, T. Besset and F. Glorius, Angew. Chem., Int. Ed., 2011, 20 S. Zhang, F. Song, D. Zhao and J. You, Chem. Commun., 2013, 49, 4558.
0, 1064; (b) S. Rakshit, C. Grohmann, T. Besset and F. Glorius, J. Am. 21 K. Kapłon, O. M. Demchuk, M. Wieczorek and K. M. Pietrusiewicz,
Chem. Soc., 2011, 133, 2350; (c) C. Wang, H. Chen, Z. Wang, J. Chen and Curr. Chem. Lett., 2014, 3, 23.
This journal is ©The Royal Society of Chemistry 2014
Chem. Commun.