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Synlett 2016; 27(13): 2029-2033
DOI: 10.1055/s-0035-1562432
DOI: 10.1055/s-0035-1562432
letter
Synthesis of Trifluoromethyl-Substituted Ethyl Picolinate Derivatives by the Cobalt-Catalyzed Regioselective Intermolecular [2+2+2] Cycloaddition
Further Information
Publication History
Received: 23 April 2016
Accepted after revision: 09 May 2016
Publication Date:
14 June 2016 (online)
Abstract
We demonstrated the intermolecular [2+2+2] cycloaddition of aryl- and trifluoromethyl-substituted internal alkyne and ethyl cyanoformate, and succeeded in constructing the pyridine derivatives using the CoI2/dcype/Zn catalyst system. The reaction proceeded with a high regioselectivity, and two trifluoromethyl-substituted ethyl picolinate derivatives were obtained as a single regioisomer.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1562432.
- Supporting Information
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- 18 The reaction provided detectable amount of benzene derivative, which was formed by the trimerization of 1a, as a side product.
- 19 General Procedure for the Cobalt-Catalyzed [2+2+2] Cycloaddition of Aryl- and Trifluoromethyl-Substituted Internal Alkynes 1 and Ethyl Cyanoformate (2) A typical procedure is given for the reaction of 1-(4-methoxyphenyl)-3,3,3-trifluoropropyne (1a) with ethyl cyanoformate (2, Table 1, entry 14). CoI2 (19 mg, 0.061 mmol) and dcype (51 mg, 0.121 mmol) were suspended in 0.6 mL of THF, and the mixture was stirred at room temperature for 5 min. Alkyne 1a (121 mg, 0.605 mmol), ethyl cyanoformate (2, 30 mg, 0.303 mmol), and Zn powder (24 mg, 0.367 mmol) were added to the reaction mixture, then stirred at 60 °C for 16 h. The reaction mixture was diluted with EtOAc, and the mixture was passed through a pad of silica gel and Florisil, then the filtrate was concentrated in vacuo. The NMR yield (C6H5CF3 as an internal standard) was determined to be 94% yield. The residue was chromatographed on silica gel (hexane–Et2O, 7:3) to give 139 mg (92%) of 3a as a white solid; mp 151–153 °C. 1H NMR (500 MHz, CDCl3): δ = 1.44 (t, J = 6.3 Hz, 3 H), 2.26 (s, 6 H), 4.52 (q, J = 6.3 Hz, 2 H), 6.81 (d, J = 6.3 Hz, 4 H), 6.97 (d, J = 6.3 Hz, 4 H). 13C NMR (125 Hz, CDCl3): δ = 13.9, 55.1, 63.0, 113.0, 120.2 (q, J CF = 277.1 Hz), 122.3 (q, J CF = 275.9 Hz), 124.7, 124.8 (q, J CF = 29.6 Hz), 126.2, 130.1, 130.9, 139.1, 148.0 (q, J CF = 33.4 Hz), 148.7, 154.0, 159.2, 159.3, 165.3. 19F NMR (470 MHz, CDCl3): δ = 99.8 (s, 3 F), 107.7 (s, 3 F). IR (KBr): 2969, 2941, 2841, 1757, 1611, 1519, 1031, 626, 552 cm–1. ESI-HRMS: m/z calcd for C24H20F6NO4 [M + H]+: 500.1291; found: 500.1320
- 20 We recovered unreacted 1k and 1l in 75% NMR yield and 86% NMR yield, respectively. These results suggest that the coordination of alkynes to cobalt or formation of the cobaltcyclopentadiene (complex I in Scheme 1) is very slow.