1,2-Addition of Phenylacetylene to Aldimines Catalyzed by InCl₃/CuCl in Water under Barbier Conditions

Abstract

A new and efficient method for the preparation of various propargylamines has been achieved by the simple Barbier-Grignard-type reaction of phenylacetylene with a variety of ald­imines under aqueous conditions, catalyzed by a bimetallic In-Cu system.

aldimines - water - indium chloride - copper chloride - propargylamines

References and Notes

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20

General Experimental Procedure for the Addition of Alkynes 1 to Aldimines 2 Aldimine 1a (0.225 g, 1 mmol) in a round-bottomed flask was treated with InCl₃ (0.0026 g, 1.2 mol%), CuCl (0.120 g, 12 mol%), phenyl acetylene (0.12 g, 1.2 mmol), and H₂O (2 mL). The mixture was then stirred at r.t. for 20 min and then at 40 ˚C for 4 h. Stirring was continued until no further increase of the reaction product as monitored by ^¹H NMR. After completion, the product was extracted with Et₂O or EtOAc (3 × 30 mL). The combined organic layers were washed with H₂O and dried over anhyd Na₂SO₄. Evaporation of the solvent gave a crude product which was subjected to column chromatography on silica gel with EtOAc-hexane (1:6) as eluent to afford exclusively the corresponding propargylamine 3a in 85% yield.
Conpound 3b: IR (liquid film): ν_max = 3410, 2230, 1615, 1510, 1325, 1185 cm^{- ¹}. ^¹H NMR (300 MHz, CDCl₃): δ = 2.20 (s, 3 H), 4.12 (br, 1 H), 5.21 (s, 1 H), 6.84-7.01 (m, 3 H), 7.18-7.36 (m, 7 H), 7.40-7.48 (m, 2 H), 7.62 (d, J = 8.5 Hz, 2 H). ^{¹ ³}C NMR (75 MHz, CDCl₃): δ = 21.3, 50.6, 85.2, 89.0, 115.1, 119.2, 123.1, 127.5, 128.3, 128.5, 129.3, 129.6, 132.1, 137.2, 138.2, 146.8. MS: m/z = 297 [M⁺].

Compound 3h: mp 185-86 ˚C. ^¹H NMR (300 MHz, CDCl₃): δ = 2.24 (s, 3 H), 4.83 (br, 1 H), 5.48 (d, 1 H), 7.18-7.24
(m, 2 H), 7.32-7.48 (m, 8 H), 7.59-7.65 (m, 2 H), 7.76 (d, J = 8.5 Hz, 2 H). ^{¹ ³}C NMR (75 MHz, CDCl₃): δ = 21.4, 50.1, 85.6, 87.2, 120.0, 127.2, 127.6, 128.2, 128.6, 128.8, 129.0, 129.6, 131.5, 137.4, 137.8, 144.5. MS: m/z = 361 [M⁺].
Compound 3j: mp 192-193 ˚C, ^¹H NMR (300 MHz, CDCl₃): δ = 2.28 (s, 3 H), 2.34 (s, 3 H), 4.82 (br, 1 H), 5.42 (d, 1 H), 7.10-7.31 (m, 9 H), 7.38 (d, J = 8.5 Hz, 2 H), 7.68 (d, J = 8.5 Hz, 2 H). ^{¹ ³}C NMR (75 MHz, CDCl₃): δ = 21.3, 21.7, 50.2, 85.6, 87.0, 121.3, 127.1, 127.8, 128.4, 129.0, 129.2, 129.8, 130.2, 132.0, 136.2, 137.4, 138.6, 145.8. MS: m/z = 375 [M⁺].
Compound 3k: mp 197-199 ˚C. ^¹H NMR (300 MHz, CDCl₃): δ = 2.33 (s, 3 H), 4.80 (br, 1 H), 5.50 (d, 1 H), 7.19-7.42 (m, 10 H), 7.55 (d, J = 8.5 Hz, 2 H), 7.70 (d, J = 8.5 Hz, 2 H). ^{¹ ³}C NMR (75 MHz, CDCl₃): δ = 21.8, 49.8, 85.6, 87.0, 121.2, 127.0, 127.8, 128.4, 128.6, 129.1, 129.2, 129.8, 130.2, 132.1, 136.2, 137.3, 138.6, 145.8. MS: m/z = 361 [M⁺].

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