Synthesis of Trifluoromethyl-Substituted Ethyl Picolinate Derivatives by the Cobalt-Catalyzed Regioselective Intermolecular [2+2+2] Cycloaddition

Tomoki Ishikawa; Taro Sonehara; Shogo Murakami; Maki Minakawa; Motoi Kawatsura

doi:10.1055/s-0035-1562432

Synlett, Table of Contents

Synlett 2016; 27(13): 2029-2033
DOI: 10.1055/s-0035-1562432

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Synthesis of Trifluoromethyl-Substituted Ethyl Picolinate Derivatives by the Cobalt-Catalyzed Regioselective Intermolecular [2+2+2] Cycloaddition

Tomoki Ishikawa

Department of Chemistry, College of Humanities & Sciences, Nihon University, Sakurajosui, Setagaya-ku, Tokyo 156-8550, Japan Email: kawatsur@chs.nihon-u.ac.jp

,

Taro Sonehara

Department of Chemistry, College of Humanities & Sciences, Nihon University, Sakurajosui, Setagaya-ku, Tokyo 156-8550, Japan Email: kawatsur@chs.nihon-u.ac.jp

,

Shogo Murakami

Department of Chemistry, College of Humanities & Sciences, Nihon University, Sakurajosui, Setagaya-ku, Tokyo 156-8550, Japan Email: kawatsur@chs.nihon-u.ac.jp

,

Maki Minakawa

Department of Chemistry, College of Humanities & Sciences, Nihon University, Sakurajosui, Setagaya-ku, Tokyo 156-8550, Japan Email: kawatsur@chs.nihon-u.ac.jp

,

Motoi Kawatsura*

Department of Chemistry, College of Humanities & Sciences, Nihon University, Sakurajosui, Setagaya-ku, Tokyo 156-8550, Japan Email: kawatsur@chs.nihon-u.ac.jp

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Abstract

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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.

Key words

cobalt - cycloaddition - fluorine - pyridines - nitriles - alkynes

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References

References and Notes

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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.

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