Synthesis of 1,3,5-Trisubstituted Pyrazoles by the Cope-Type Hydroamination of 1,3-Dialkynes with Alkylhydrazines

Xiaoqiang Yu; Nan Huang; Xiujuan Feng; Yoshinori Yamamoto; Ming Bao

doi:10.1055/s-0034-1378660

Synthesis, Table of Contents

Synthesis 2014; 46(18): 2422-2429
DOI: 10.1055/s-0034-1378660

feature article

Synthesis of 1,3,5-Trisubstituted Pyrazoles by the Cope-Type Hydroamination of 1,3-Dialkynes with Alkylhydrazines

Xiaoqiang Yu*

^aState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, P. R. of China Fax: +86(411)84986180 Email: yuxiaoqiang@dlut.edu.cn Email: mingbao@dlut.edu.cn

,

Nan Huang

^aState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, P. R. of China Fax: +86(411)84986180 Email: yuxiaoqiang@dlut.edu.cn Email: mingbao@dlut.edu.cn

,

Xiujuan Feng

^aState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, P. R. of China Fax: +86(411)84986180 Email: yuxiaoqiang@dlut.edu.cn Email: mingbao@dlut.edu.cn

,

Yoshinori Yamamoto

^aState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, P. R. of China Fax: +86(411)84986180 Email: yuxiaoqiang@dlut.edu.cn Email: mingbao@dlut.edu.cn

^bWPI-AIMR (WPI-Advanced Institute for Materials Research), Tohoku University, Sendai 980-8577, Japan

,

Ming Bao*

^aState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, P. R. of China Fax: +86(411)84986180 Email: yuxiaoqiang@dlut.edu.cn Email: mingbao@dlut.edu.cn

› Author Affiliations

Abstract

All articles of this category

Abstract

An efficient method to synthesize 1,3,5-trisubstituted pyrazoles was developed. The reaction of 1,3-dialkynes with alkylhydrazines smoothly proceeded in dimethyl sulfoxide under suitable heating conditions to produce 1,3,5-trisubstituted pyrazoles in satisfactory to excellent yields.

Key words

1,3,5-trisubstituted pyrazole - 1,3-dialkyne - alkylhydrazine - synthesis - Cope-type hydroamination

Full Text

References

References

1a Stauffer SR, Coletta CJ, Tedesco R, Nishiguchi G, Carlson K, Sun J, Katzenellenbogen BS, Katzenellenbogen JA. J. Med. Chem. 2000; 43: 4934
1b Stauffer SR, Huang Y, Coletta CJ, Tedesco R, Katzenellenbogen JA. Bioorg. Med. Chem. 2001; 9: 141

2 Tanitame A, Oyamada Y, Ofuji K, Fujimoto M, Suzuki K, Ueda T, Terauchi H, Kawasaki M, Nagai K, Wachi M, Yamagishi J.-I. Bioorg. Med. Chem. 2004; 12: 5515
3 Katoch-Rouse R, Pavlova LA, Caulder T, Hoffman AF, Mukhin AG, Horti AG. J. Med. Chem. 2003; 46: 642

4a Bekhit AA, Abdel-Aziem T. Bioorg. Med. Chem. 2004; 12: 1935
4b Selvam C, Jachak SM, Thilagavathi R, Chakraborti AK. Bioorg. Med. Chem. Lett. 2005; 15: 1793

For the reaction of hydrazine with a three-carbon-atom component, see:

5a Baxendale IR, Schou SC, Sedelmeier J, Ley SV. Chem. Eur. J. 2010; 16: 89
5b Chen X, She J, Shang Z.-C, Wu J, Zhang P. Synth. Commun. 2009; 39: 947 ; and references cited therein
5c Guillou S, Bonhomme FJ, Janin YL. Synthesis 2008; 3504
5d Chen X, She J, Shang Z, Wu J, Wu H, Zhang P. Synthesis 2008; 3478
5e Liu H.-L, Jiang H.-F, Zhang M, Yao W.-J, Zhu Q.-H, Tang Z. Tetrahedron Lett. 2008; 49: 3805
5f Bagley MC, Lubinu MC, Mason C. Synlett 2007; 704
5g Negri G, Kascheres C. J. Heterocycl. Chem. 2001; 38: 109 ; and references cited therein
5h Sreekumar R, Padmakumar R. Synth. Commun. 1998; 28: 1661
5i Trxier-Boullet F, Hamelin BK. J. Synthesis 1986; 409

For the [3+2] cycloaddition of alkenes/alkynes with 1,3-dipoles, see:

6a Dadiboyena S, Valente EJ, Hamme AT. Tetrahedron Lett. 2010; 51: 1341
6b Gao D, Zhai H, Parvez M, Back TG. J. Org. Chem. 2008; 73: 8057
6c Deng X, Mani NS. J. Org. Chem. 2008; 73: 2412 ; and references cited therein
6d Aggarwal VK, Vicente J, Bonnert RV. J. Org. Chem. 2003; 68: 5381 ; and references cited therein
6e Padwa A, Pearson WH. Synthetic Applications of 1,3-Dipolar Cycloaddition Chemistry Toward Heterocycles and Natural Products. Wiley; New York: 2002

For the transition-metal-catalyzed cross-coupling reactions, see:

7a Martin R, Rodriguez Rivero M, Buchwald SL. Angew. Chem. Int. Ed. 2006; 45: 7079 ; Angew. Chem. 2006, 118, 7237
7b Zhang T, Bao W. J. Org. Chem. 2013; 78: 1317
7c Hu J, Chen S, Sun Y, Yang J, Rao Y. Org. Lett. 2012; 14: 5030

8 Wang L, Yu X, Feng X, Bao M. J. Org. Chem. 2013; 78: 1693

9a Botana LM, Peinador C, Quintela JM, Riguera R, Moreira MJ, Alfonso A. Eur. J. Med. Chem. 2001; 36: 321
9b Wang ZX, Zhao ZG. J. Heterocycl. Chem. 2007; 44: 89

10 The structural assignment was based on the analysis of the ¹H and ¹³C NMR spectra. The unsymmetrical product was further identified by determining its X-ray crystal structure; the crystallographic data are provided in the Supporting Information.

For the Cu-catalyzed homocoupling reaction of alkynes, see:

11a Niu X, Li C, Li J, Jia X. Tetrahedron Lett. 2012; 53: 5559
11b Li Y.-N, Wang J.-L, He L.-N. Tetrahedron Lett. 2011; 52: 3485
11c Yin K, Li C, Li J, Jia X. Green Chem. 2011; 13: 591
11d Wang D, Li J, Li N, Gao T, Hou S, Chen B. Green Chem. 2010; 12: 45 ; and references cited therein

12 Mizunoa N, Kamata K, Nakagawa Y, Oishia T, Yamaguchi K. Catal. Today. 2010; 157: 359
13 Serwinski PR, Lahti PM. Org. Lett. 2003; 5: 2099
14 Alonso F, Melkonian T, Moglie Y, Yus M. Eur. J. Org. Chem. 2011; 2524
15 Yu M, Pan D, Jia W, Chen W, Jiao N. Tetrahedron Lett. 2010; 51: 1287
16 Kondo K, Fujitanib T, Onishi N. J. Mater. Chem. 1997; 7: 429
17 Muller TJ. J, Blumel J. J. Organomet. Chem. 2003; 683: 354
18 Nie X, Wang G. J. Org. Chem. 2006; 71: 4734

Supplementary Material

Supporting Information