Synlett 2015; 26(01): 59-62
DOI: 10.1055/s-0034-1378937
cluster
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Trifluoromethylated Cycloheptatrienes from N-Tosylhydrazones: Transition-Metal-Free Büchner Ring Expansion

Zhikun Zhang
a  Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, P. R. of China   Fax: +86(10)62751708   Email: wangjb@pku.edu.cn
,
Jiajie Feng
a  Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, P. R. of China   Fax: +86(10)62751708   Email: wangjb@pku.edu.cn
,
Yan Xu
a  Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, P. R. of China   Fax: +86(10)62751708   Email: wangjb@pku.edu.cn
,
Songnan Zhang
a  Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, P. R. of China   Fax: +86(10)62751708   Email: wangjb@pku.edu.cn
,
Yuxuan Ye
a  Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, P. R. of China   Fax: +86(10)62751708   Email: wangjb@pku.edu.cn
,
Tianjiao Li
a  Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, P. R. of China   Fax: +86(10)62751708   Email: wangjb@pku.edu.cn
,
Xi Wang*
a  Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, P. R. of China   Fax: +86(10)62751708   Email: wangjb@pku.edu.cn
,
Jun Chen
b  Beijing Institute of Microchemistry, No.15 Xinjiangongmen Road, Haidian District, Beijing, 100091, P. R. of China
,
Yan Zhang
a  Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, P. R. of China   Fax: +86(10)62751708   Email: wangjb@pku.edu.cn
,
Jianbo Wang*
a  Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, P. R. of China   Fax: +86(10)62751708   Email: wangjb@pku.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 30 September 2014

Accepted after revision: 21 October 2014

Publication Date:
18 November 2014 (online)

Abstract

A transition-metal-free Büchner reaction using trifluoromethylated N-tosylhydrazones as substrates is reported. A series of trifluoromethylated cycloheptatriene derivatives can be synthesized by this straightforward method.

Supporting Information

 
  • References and Notes


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  • 11 General Procedure for the Büchner ReactionIn an oven-dried 20 mL Schlenk tube, N-tosylhydrazone (1, 0.2 mmol, 1.0 equiv), Cs2CO3 (0.6 mmol, 3 equiv), and 4 Å MS were added. Then the tube was sealed with a septum, and degassed by alternating vacuum evacuation and nitrogen backfill (3×) before benzene (4 mL) was added. The reaction was then stirred at 120 °C for 3 h. The reaction mixture was cooled to r.t. and filtered through a short plug of silica gel with Et2O as eluents. Solvent was then removed in vacuo to leave a crude mixture, which was purified by preparative TLC to afford pure products.7-Phenyl-7-(trifluoromethyl)cyclohepta-1,3,5-triene (3a) 1H NMR (400 MHz, CDCl3): δ = 7.26 (d, J = 7.4 Hz, 2 H), 7.18–7.09 (m, 3 H), 6.44–6.42 (m, 2 H), 6.30–6.28 (m, 2 H), 5.72 (d, J = 9.3 Hz, 2 H). 13C NMR (101 MHz, CDCl3): δ = 134.9, 130.2, 129.8, 127.8, 127.1 (q, J = 281.9 Hz), 126.6, 126.6, 117.3, 53.2 (q, J = 25.0 Hz). 19F NMR (470 MHz, CDCl3): δ = –74.3 (s, 3 F). MS (EI): m/z (%) = 236 (66) [M+], 215 (15), 167 (100), 165 (60), 152 (28). IR (film): 1284, 1188, 1151, 978, 687 cm–1. HRMS (EI): m/z calcd for C14H11F3 [M]+: 236.0807; found: 236.0815.