Organic Letters
Letter
R. Adv. Synth. Catal. 2005, 347, 1987−1992. (c) Brutchey, R. L.;
Drake, I. J.; Bell, A. T.; Tilley, T. D. Chem. Commun. 2005, 29, 3736−
Scheme 4. Plausible Mechanism of Successive C−H
Functionalizations of Methyl Group
3738. (d) Backvall, J.-E. Modern Oxidation Methods; Wiley−VCH:
̈
Weinheim, 2003; pp 1−336.
(5) Vanjari, R.; Singh, K. N. Chem. Soc. Rev. 2015, 44, 8062−8096.
(6) Andrushkevich, T. V.; Ovchinnikova, E. V. Catal. Rev.: Sci. Eng.
2012, 54, 399−436.
(7) Wang, Y.; Yamaguchi, K.; Mizuno, N. Angew. Chem. 2012, 124,
7362−7365.
(8) Guo, S.; Wan, G.; Sun, S.; Jiang, Y.; Yu, J.-T.; Cheng, J. Chem.
Commun. 2015, 51, 5085−5088.
(9) Wang, L.; Cao, J.; Chen, Q.; He, M.-Y. Tetrahedron Lett. 2014,
55, 7190−7193.
In conclusion, an intramolecular carbonylation of arenes via
oxidative C−H functionalizations of a methyl group present in
2-aryl-3-picolines has been developed, providing an expedient
access to 4-azafluorenones. The current study complements the
literature protocol, wherein a carboxylic ester or acid group is
converted to the carbonyl group using classical chemistry. The
protocol unveils a new strategy for the intramolecular oxidative
heteroaroylation of arenes via successive C−H functionaliza-
tions of a methyl or hydroxymethyl group present on pyridine.
(10) (a) Mueller, D.; Davis, R. A.; Duffy, S.; Avery, V. M.; Camp, D.;
Quinn, R. J. J. Nat. Prod. 2009, 72, 1538−1540. (b) Kraus, G. A.;
Kempema, A. J. Nat. Prod. 2010, 73, 1967−1968. (c) Wijeratne, E. M.
K.; De Silva, L. B. J. Nat. Prod. 1995, 58, 459−462.
(11) Stauffer, K. J.; Williams, P. D.; Selnick, H. G.; Nantermet, P. G.;
Newton, C. L.; Homnick, C. F.; Zrada, M. M.; Lewis, S. D.; Lucas, B.
J.; Krueger, J. A.; Pietrak, B. L.; Lyle, E. A.; Singh, R.; Miller-Stein, C.;
White, R. B.; Wong, B.; Wallace, A. A.; Sitko, G. R.; Cook, J. J.;
Holahan, M. A.; Stranieri-Michener, M.; Leonard, Y. M.; Lynch, J. J.;
McMasters, D. R.; Yan, Y. J. Med. Chem. 2005, 48, 2282−2293.
(12) (a) Hwu, T.-Y.; Tsai, T.-C.; Hung, W.-Y.; Chang, S.-Y.; Chi, Y.;
Chen, M.-H.; Wu, C.-I.; Wong, K.-T.; Chi, L.-C. Chem. Commun.
2008, 40, 4956−4958. (b) Wong, K.-T.; Hwu, T.-Y.; Balaiah, A.; Chao,
T.-C.; Fang, F.-C.; Lee, C.-T.; Peng, Y.-C. Org. Lett. 2006, 8, 1415−
1418.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
(13) Prostakov, N. S.; Soldatenkov, A. T.; Kolyadina, N. M.;
Obynochnyi, A. A. Russ. Chem. Rev. 1997, 66, 121−138.
́ ́
(14) (a) Rebstock, A.-S.; Mongin, F.; Trecourt, F.; Queguiner, G.
Tetrahedron 2003, 59, 4973−4977. (b) DuPriest, M. T.; Schmidt, C.
L.; Kuzmich, D.; Williams, S. B. J. Org. Chem. 1986, 51, 2021−2023.
(15) (a) Sreekumar, R.; Rugmini, P.; Padmakumar, R. Synth.
Commun. 1998, 28, 2071−2075. (b) Zhang, S.; Liao, L.-Y.; Zhang,
F.; Duan, X.-F. J. Org. Chem. 2013, 78, 2720−2725.
(16) (a) Dhara, S.; Ahmed, A.; Nandi, S.; Baitalik, S.; Ray, J. K.
Tetrahedron Lett. 2013, 54, 63−65. (b) Marquise, N.; Dorcet, V.;
Chevallier, F.; Mongin, F. Org. Biomol. Chem. 2014, 12, 8138−8148.
(c) Marquise, N.; Harford, P. J.; Chevallier, F.; Roisnel, T.; Wheatley,
A. E. H.; Gros, P. C.; Mongin, F. Tetrahedron Lett. 2013, 54, 3154−
3157. (d) Marquise, N.; Harford, P. J.; Chevallier, F.; Roisnel, T.;
Dorcet, V.; Gagez, A.-L.; Sable, S.; Picot, L.; Thiery, V.; Wheatley, A.
E. H.; Gros, P. C.; Mongin, F. Tetrahedron 2013, 69, 10123−10133.
(17) (a) Tu, S.; Jiang, B.; Jiang, H.; Zhang, Y.; Jia, R.; Zhang, J.; Shao,
Q.; Li, C.; Zhou, D.; Cao, L. Tetrahedron 2007, 63, 5406−5414.
(b) Tu, S.; Jiang, B.; Jia, R.; Zhang, J.; Zhang, Y. Tetrahedron Lett.
2007, 48, 1369−1374.
Experimental procedures, characterization data of new
1
compounds, and copies of H and 13C NMR spectra
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We greatly appreciate the Science & Engineering Research
Board (SERB) of DST, New Delhi for financial support. KPJ
thanks the NIPER S.A.S. Nagar for a research fellowship.
REFERENCES
■
(18) Alessi, M.; Larkin, A. L.; Ogilvie, K. A.; Green, L. A.; Lai, S.;
Lopez, S.; Snieckus, V. J. Org. Chem. 2007, 72, 1588−1594.
(19) (a) Shi, Z.; Glorius, F. Chem. Sci. 2013, 4, 829−833. (b) Wertz,
S.; Leifert, D.; Studer, A. Org. Lett. 2013, 15, 928−931.
(20) Laha, J. K.; Jethava, K. P.; Dayal, N. J. Org. Chem. 2014, 79,
8010−8019.
(1) For recent reviews on CDC, see: (a) Topczewski, J. J.; Sanford,
M. S. Chem. Sci. 2015, 6, 70−76. (b) Wu, Y.; Wang, J.; Mao, F.;
Kwong, F. Y. Chem. - Asian J. 2014, 9, 26−47. (c) Girard, S. A.;
Knauber, T.; Li, C.-J. Angew. Chem., Int. Ed. 2014, 53, 74−100.
(d) Yoshikai, N.; Wei, Y. Asian J. Org. Chem. 2013, 2, 466−478.
(e) Zhang, C.; Tang, C.; Jiao, N. Chem. Soc. Rev. 2012, 41, 3464−3484.
(f) Cho, S. H.; Kim, J. Y.; Kwak, J.; Chang, S. Chem. Soc. Rev. 2011, 40,
5068−5083. (g) Yeung, C. S.; Dong, V. M. Chem. Rev. 2011, 111,
1215−1292. (h) Scheuermann, C. J. Chem. - Asian J. 2010, 5, 436−
451.
(21) Laha, J. K.; Dayal, N.; Jethava, K. P.; Prajapati, D. V. Org. Lett.
2015, 17, 1296−1299.
(22) Laha, J. K.; Dayal, N. Org. Lett. 2015, 17, 4742−4745.
(23) (a) Ali, W.; Behera, A.; Guin, S.; Patel, B. K. J. Org. Chem. 2015,
80, 5625−5632. (b) Wu, X.-F.; Gong, J.-L.; Qi, X. Org. Biomol. Chem.
2014, 12, 5807−5817.
(2) (a) Franzoni, I.; Mazet, C. Org. Biomol. Chem. 2014, 12, 233−
241. (b) Jia, C.; Kitamura, T.; Fujiwara, Y. Acc. Chem. Res. 2001, 34,
633−639.
(24) Kim, J. Y.; Park, S. H.; Ryu, J.; Cho, S. H.; Kim, S. H.; Chang, S.
J. Am. Chem. Soc. 2012, 134, 9110−9113.
(3) (a) Li, H.; Li, B.-J.; Shi, Z.-J. Catal. Sci. Technol. 2011, 1, 191−
206. (b) Jazzar, R.; Hitce, J.; Renaudat, A.; Sofack-Kreutzer, J.;
Baudoin, O. Chem. - Eur. J. 2010, 16, 2654−2672. (c) Li, Z.; Bohle, D.
S.; Li, C.-J. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 8928−8933.
(4) (a) Kesavan, L.; Tiruvalam, R.; Ab Rahim, M. H.; bin Saiman, M.
I.; Enache, D. I.; Jenkins, R. L.; Dimitratos, N.; Lopez-Sanchez, J. A.;
Taylor, S. H.; Knight, D. W.; Kiely, C. J.; Hutchings, G. J. Science 2011,
331, 195−199. (b) Wang, F.; Xu, J.; Li, X.; Gao, J.; Zhou, L.; Ohnishi,
D
Org. Lett. XXXX, XXX, XXX−XXX