Cobalt-Catalyzed Direct Alkenylation of 2-Methylquinolines with Aldehydes via C(sp3)–H Functionalization in Water

Zaini Jamal; Yong-Chua Teo

doi:10.1055/s-0034-1378355

Synlett, Table of Contents

Synlett 2014; 25(14): 2049-2053
DOI: 10.1055/s-0034-1378355

letter

Cobalt-Catalyzed Direct Alkenylation of 2-Methylquinolines with Aldehydes via C(sp³)–H Functionalization in Water

Zaini Jamal

Natural Sciences and Science Education, National Institute of Education, Nanyang Technological University, Singapore 637616, Singapore Fax: +6568969414 Email: yongchua.teo@nie.edu.sg

,

Yong-Chua Teo*

Natural Sciences and Science Education, National Institute of Education, Nanyang Technological University, Singapore 637616, Singapore Fax: +6568969414 Email: yongchua.teo@nie.edu.sg

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Abstract

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Abstract

The direct C(sp³)–H alkenylation of 2-methylquinolines with aldehydes as a simple methodology to afford 2-alkenylated quinolines is reported. In the presence of catalytic CoCl₂ in water, the economically and ecologically sound transformation is proposed to proceed via the direct benzylic addition to the aldehyde followed by an elimination step to provide 2-alkenylated quinolines in good to excellent yield of up to 95%.

Key words

aldehydes - alkenylation - aza-arenes - C–H functionalization - cobalt

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References

References and Notes

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10 General Procedure To an 8 mL screw-capped reaction vial equipped with a magnetic stirrer bar, CoCl₂ (1.3 mg, 2.0 mol%), 2-methyl-quinoline (0.5 mmol), aldehyde (1.0 mmol), and H₂O (0.3 mL) were added. The resulting mixture was placed into a preheated oil bath at 120 °C with vigorous stirring. After 24 h, the reaction mixture was removed from the oil bath, allowed to cool to r.t. and poured into H₂O (10 mL). The mixture was then extracted with EtOAc (3 × 20 mL), washed with brine (40 mL), dried over Na₂SO₄, filtered, and the solvent removed under reduced pressure. The crude product was then loaded onto a column of silica gel suspended in hexane. Purification by flash chromatography (hexane–EtOAc = 95:5, v/v) then gave the pure alkenylation product. (E)-2-(4-Bromostyryl)quinoline (3ad) Pale yellow solid in 91% yield (141.8 mg). ¹H NMR (400 MHz, CDCl₃): δ = 8.08 (d, J = 8.4 Hz, 2 H), 7.76 (d, J = 8.0 Hz, 1 H), 7.70 (t, J = 7.62 Hz, 1 H), 7.62–7.58 (m, 2 H), 7.51–7.45 (m, 5 H), 7.35 (d, J = 16.4 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 155.6, 148.3, 136.5, 135.5, 133.1, 132.0, 129.9, 129.7, 129.3, 128.7, 127.5, 127.4, 126.3, 122.6, 119.4. ESI-HRMS: m/z calcd for C₁₇H₁₃BrN [M + H]: 310.0231; found: 310.0234. (E)-2-[2-(Pyridin-3-yl)vinyl]quinoline (5ad) Pale yellow solid in 86% yield (100.2 mg). ¹H NMR (400 MHz, CDCl₃): δ = 8.83 (s, 1 H), 8.54 (s, 1 H), 8.10 (dd, J ₁ = 8.4 Hz, J ₂ = 12.2 Hz, 2 H), 7.92 (d, J = 8.0 Hz, 1 H), 7.78–7.61 (m, 4 H), 7.50 (t, J = 7.4 Hz, 1 H), 7.42 (d, J = 16.4 Hz, 1 H), 7.30 (dd, J ₁ = 5.2 Hz, J ₂ = 8.0 Hz 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 155.2, 149.4, 149.2, 148.2, 136.6, 133.3, 132.3, 130.9, 130.6, 129.9, 129.3, 127.55, 127.52, 126.5, 123.7, 119.4. ESI-HRMS: m/z calcd for C₁₆H₁₃N₂ [M + H]: 233.1078; found: 233.1075. (E)-8-Chloro-2-styrylquinoline (3da) This compound was prepared in a similar procedure to the general procedure with 5.0 mol% CoCl₂ at 140 °C for 48 h to afford a pale yellow solid in 84% yield (111.3 mg). ¹H NMR (400 MHz, CDCl₃): δ = 8.09 (d, J = 8.8 Hz, 1 H), 7.81 (dd, J ₁ = 1.0 Hz, J ₂ = 7.4 Hz, 1 H), 7.75 (d, J = 16.4 Hz, 1 H), 7.70–7.64 (m, 4 H), 7.48–7.32 (m, 5 H). ¹³C NMR (100 MHz, CDCl₃): δ = 156.6, 144.4, 136.6, 136.3, 135.3, 133.3, 129.8, 128.8, 128.75, 128.73, 128.5, 127.4, 126.6, 125.9, 120.0. ESI-HRMS: m/z calcd for C₁₇H₁₃ClN [M + H]: 266.0736; found: 266.0739.

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