A New Synthetic Route to (Trifluoromethyl)quinolines: Nickel-Catalyzed Insertion of an Alkyne into an Aromatic C–S Bond by Formation of a Thianickelacycle and Thermal Desulfidation

Tasuku Inami; Takuya Kurahashi; Seijiro Matsubara

doi:10.1055/s-0037-1610785

Synlett, Table of Contents

Synlett 2021; 32(19): 1948-1952
DOI: 10.1055/s-0037-1610785

letter

A New Synthetic Route to (Trifluoromethyl)quinolines: Nickel-Catalyzed Insertion of an Alkyne into an Aromatic C–S Bond by Formation of a Thianickelacycle and Thermal Desulfidation

Tasuku Inami

,

Takuya Kurahashi ∗

,

Seijiro Matsubara ∗

Abstract

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Abstract

We have developed a nickel-catalyzed insertion reaction of an alkyne into a 2-(trifluoromethyl)-1,3-benzothiazole to give a seven-membered benzothiazepine that is converted into a 2-(trifluoromethyl)quinoline by thermal desulfidation. This process can be considered a formal substitution of a sulfur atom with an alkyne. The structure of the thianickelacycle intermediate formed through oxidative addition of a C–S bond in the benzothiazole to nickel(0) was confirmed by X-ray single-crystal structure analysis and in situ X-ray absorption fine-structure spectroscopy.

Key words

nickel catalysis - cycloaddition - desulfidation - alkynes - benzothiazoles - trifluoromethylquinolines

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References

References and Notes

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8 3,4-Diisopropyl-2-(trifluoromethyl)quinoline (4aa): Typical Procedure The reaction was performed in a 5 mL sealed tube equipped with a Teflon-coated magnetic stirrer bar. Benzothiazole 1a (0.20 mmol) and alkyne 2a (0.40 mmol; 2.0 equiv) were added to a solution of bis(1,5-cyclooctadiene)nickel (5.5 mg, 0.02 mmol, 10 mol%) and IPr (15.6 mg, 0.04 mmol, 20 mol%) in hexane (0.3 mL) in a dry box. The sealed tube was removed from the dry box, and the mixture was stirred at rt for 12 h then heated at 80 °C for 3 h. The resulting mixture was cooled to rt, filtered through a pad of silica gel, and concentrated in vacuo. The residue was purified by flash column chromatography [silica gel, hexane–EtOAc (20:1)] to give a white solid; yield: 53.1 mg (94%); mp 55–57 °C. IR (KBr): 2965, 2872, 1364, 1302, 1177, 1126, 1065, 768, 740 cm^–1. ¹H NMR (500 MHx, CDCl₃): δ = 8.15 (dd, J = 8.5, 1.0 Hz, 1 H, Ar), 8.02 (dd, J = 8.5, 1.0 Hz, 1 H; Ar), 7.73–7.69 (m, 1 H, Ar), 7.65–7.62 (m, 1 H, Ar), 3.12–3.09 (m, 2 H, CH₂ Et), 2.90–2.87 (m, 2 H, CH₂ Et), 1.73–1.60 (m, 4 H, 2CH₂CH₂ CH₃), 1.15 (t, J = 7.5 Hz, 3 H, CH₃), 1.11 (t, J = 7.5 Hz, 3 H, CH₃). ¹³C NMR (125.7 MHz, CDCl₃): δ = 149.3, 146.2 (q, J = 31 Hz), 145.0, 130.9, 130.4, 129.1, 128.2, 123.6, 122.4 (q, J = 275 Hz), 30.5 (d, J = 2.4 Hz), 30.2, 24.9, 24.3, 14.80, 14.78. ¹⁹F NMR (188 Hz, CDCl₃): δ = –64.1. HRMS (ESI+): m/z [M + H]⁺ calcd for C₁₆H₁₉F₃N: 282.1464; found: 282.1460.

Supplementary Material