10.1002/ejoc.201800166
European Journal of Organic Chemistry
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C−H activation
Hyeri Ha, Changhoon Shin, Seri Bae
and Jung Min Joo*
Page No. – Page No.
Divergent Palladium-Catalyzed Cross-
Coupling of Nitropyrazoles with
Terminal Alkynes
Homo-coupling of terminal alkynes, which provides conjugated diynes, was
incorporated into a sequential process to couple with nitropyrazoles with high regio-
and stereoselectivity. Direct C−H alkynylation was achieved by carefully controlling
the stoichiometry of the catalysts, alkynes, and oxidants.
[1]
a) V. P. Boyarskiy, D. S. Ryabukhin, N. A. Bokach, A. V. Vasilyev, Chem.
Rev. 2016, 116, 5894-5986; b) R. Chinchilla, C. Nájera, Chem. Rev.
2014, 114, 1783-1826; c) B. M. Trost, C.-J. Li in Modern Alkyne
Chemistry, Wiley-VCH, 2014.
[13] A single example of directing group-assisted hydroarylation of 1,4-
diphenylbuta-1,3-diyne has been reported, where the regioselectivity
opposite to 2 was proposed. L. Liang, S. Fu, D. Lin, X.-Q. Zhang, Y. Deng,
H. Jiang, W. Zeng, J. Org. Chem. 2014, 79, 9472-9480.
[2]
[3]
a) B. M. Trost, J. T. Masters, Chem. Soc. Rev. 2016, 45, 2212-2238; b)
W. Shi, A. Lei, Tetrahedron Lett. 2014, 55, 2763-2772.
[14] For a tandem reaction involving 1:2 coupling between benzoquinones
and terminal alkynes, see: S. S. Ichake, A. Konala, V. Kavala, C.-W. Kuo,
C.-F. Yao, Org. Lett. 2017, 19, 54-57.
For reviews about C−H alkynylation, see: a) A. S. Dudnik, V. Gevorgyan,
Angew. Chem. Int. Ed. 2010, 49, 2096-2098; Angew. Chem. 2010, 122,
2140-2142; b) S. Messaoudi, J.-D. Brion, M. Alami, Eur. J. Org. Chem.
2010, 6495-6516.
[15] a) L. Yet, Pyrazoles. In Comprehensive Heterocyclic Chemistry; A. R.
Katritzky, C. A. Ramsden, E. F. V. Scriven, R. J. K. Taylor Eds.; Elsevier:
Oxford, U.K., 2008; Vol. 4, pp 1−141; b) M. F. Khan, M. M. Alam, G.
Verma, W. Akhtar, M. Akhter, M. Shaquiquzzaman, Eur. J. Med. Chem.
2016, 120, 170-201.
[4]
[5]
For reviews, see: a) C. S. Yeung, V. M. Dong, Chem. Rev. 2011, 111,
1215-1292; b) S. H. Cho, J. Y. Kim, J. Kwak, S. Chang, Chem. Soc. Rev.
2011, 40, 5068-5083; c) N. Kuhl, M. N. Hopkinson, J. Wencel-Delord, F.
Glorius, Angew. Chem. Int. Ed. 2012, 51, 10236-10254; Angew. Chem.
2012, 124, 10382-10401; d) C. Liu, J. Yuan, M. Gao, S. Tang, W. Li, R.
Shi, A. Lei, Chem. Rev. 2015, 115, 12138-12204.
[16] a) E. J. Hanan, A. van Abbema, K. Barrett, W. S. Blair, J. Blaney, C.
Chang, C. Eigenbrot, S. Flynn, P. Gibbons, C. A. Hurley, J. R. Kenny, J.
Kulagowski, L. Lee, S. R. Magnuson, C. Morris, J. Murray, R. M. Pastor,
T. Rawson, M. Siu, M. Ultsch, A. Zhou, D. Sampath, J. P. Lyssikatos, J.
Med. Chem. 2012, 55, 10090-10107; b) V. O. Iaroshenko, A. Gevorgyan,
O. Davydova, A. Villinger, P. Langer, J. Org. Chem. 2014, 79, 2906-
2915; c) H. Jung, S. Bae, H.-L. Jang, J. M. Joo, Bull. Korean Chem. Soc.
2014, 35, 3009-3014; d) S. Bae, H.-L. Jang, H. Jung, J. M. Joo, J. Org.
Chem. 2015, 80, 690-697; e) H.-L. Jang, H. T. Kim, E. J. Cho, J. M. Joo,
Asian J. Org. Chem. 2015, 4, 1386-1391; f) S. J. Han, H. T. Kim, J. M.
Joo, J. Org. Chem. 2016, 81, 689-698; g) Z. Yi, Y. Aschenaki, R. Daley,
S. Davick, A. Schnaith, R. Wander, D. Kalyani, J. Org. Chem. 2017, 82,
6946-6957.
For slow addition of alkynes, see: a) N. Matsuyama, M. Kitahara, K.
Hirano, T. Satoh, M. Miura, Org. Lett. 2010, 12, 2358-2361; b) L. Yang,
L. Zhao, C.-J. Li, Chem. Commun. 2010, 46, 4184-4186; c) F. Shibahara,
Y. Dohke, T. Murai, J. Org. Chem. 2012, 77, 5381-5388.
[6]
[7]
For examples of using a large excess of (hetero)arenes, see: a) Y. Wei,
H. Zhao, J. Kan, W. Su, M. Hong, J. Am. Chem. Soc. 2010, 132, 2522-
2523; b) S. H. Kim, J. Yoon, S. Chang, Org. Lett. 2011, 13, 1474-1477;
For examples of low catalyst loadings, see: X. Jie, Y. Shang, P. Hu, W.
Su, Angew. Chem. Int. Ed. 2013, 52, 3630-3633; Angew. Chem. 2013,
125, 3718-3721.
[17] Ono, N. The Nitro Group in Organic Synthesis; Wiley-VCH: New
York, 2001.
[8]
[9]
T. Kitamura, Eur. J. Org. Chem. 2009, 1111-1125.
Y. Yang, J. Lan, J. You, Chem. Rev. 2017, 117, 8787-8863.
[18] For selected recent examples of nitro group conversion, see: a) M. R.
Yadav, M. Nagaoka, M. Kashihara, R.-L. Zhong, T. Miyazaki, S. Sakaki,
Y. Nakao, J. Am. Chem. Soc. 2017, 139, 9423-9426; b) F. Inoue, M.
Kashihara, M. R. Yadav, Y. Nakao, Angew. Chem. Int. Ed. 2017, 56,
13307-13309; Angew. Chem. 2017, 129, 13492-13494; c) S. S. Bahekar,
A. P. Sarkate, V. M. Wadhai, P. S. Wakte, D. B. Shinde, Catal. Commun.
2013, 41, 123-125; d) J. Zhang, J. Chen, M. Liu, X. Zheng, J. Ding, H.
Wu, Green Chem. 2012, 14, 912-916; e) X. Zheng, J. Ding, J. Chen, W.
Gao, M. Liu, H. Wu, Org. Lett. 2011, 13, 1726-1729.
[10] M. B. Nielsen, F. Diederich, Chem. Rev. 2005, 105, 1837-1868.
[11] For examples of low selectivity in reactions with 1,3-diynes, see: a) H.
Zeng, R. Hua, J. Org. Chem. 2008, 73, 558-562; b) S. K. Ghosh, B.-C.
Kuo, H.-Y. Chen, J.-Y. Li, S.-D. Liu, H. M. Lee, Eur. J. Org. Chem. 2015,
2015, 4131-4142; c) S. Mayakrishnan, Y. Arun, C. Balachandran, N. Emi,
D. Muralidharan, P. T. Perumal, Org. Biomol. Chem. 2016, 14, 1958-
1968.
[12] Mostly, 1,3-diynes have been used in cyclization reactions to form
heterocycles by CH bond functionalization. a) D.-G. Yu, F. de Azambuja,
T. Gensch, C. G. Daniliuc, F. Glorius, Angew. Chem. Int. Ed. 2014, 53,
9650-9654; Angew. Chem. 2014, 126, 9804-9809; b) D. Y. Li, H. J. Chen,
P. N. Liu, Org. Lett. 2014, 16, 6176-6179; c) Y. Matsuda, S. Naoe, S.
Oishi, N. Fujii, H. Ohno, Chem.–Eur. J. 2015, 21, 1463-1467; d) R. Feng,
H. Ning, H. Su, Y. Gao, H. Yin, Y. Wang, Z. Yang, C. Qi, J. Org. Chem.
2017, 82, 10408-10417; e) S. Kathiravan, I. A. Nicholls, Org. Lett. 2017,
19, 4758-4761.
[19] For selected recent examples of cyclization of nitroaromatics, see: a) M.
Shevlin, X. Guan, T. G. Driver, ACS Catal. 2017, 7, 5518-5522; b) W. Fu,
K. Yang, J. Chen, Q. Song, Org. Biomol. Chem. 2017, 15, 8354-8360; c)
K. Yang, F. Zhou, Z. Kuang, G. Gao, T. G. Driver, Q. Song, Org. Lett.
2016, 18, 4088-4091.
[20] Crystallographic data for 2a have been deposited with the Cambridge
Crystallographic Data Centre as no. CCDC 1818994. Copies of the data
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