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Synlett 2015; 26(01): 59-62
DOI: 10.1055/s-0034-1378937
DOI: 10.1055/s-0034-1378937
cluster
Synthesis of Trifluoromethylated Cycloheptatrienes from N-Tosylhydrazones: Transition-Metal-Free Büchner Ring Expansion
Further Information
Publication History
Received: 30 September 2014
Accepted after revision: 21 October 2014
Publication Date:
18 November 2014 (online)
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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
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1378937.
- Supporting Information
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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.
For selected reviews, see:
For selected reviews on the reaction of diazo compounds, see: