Magnetically Recoverable Iron Nanoparticle Catalyzed Cross-Dehydrogena­tive Coupling (CDC) between Two Csp^³-H Bonds Using Molecular Oxygen

Abstract

The oxidative C-C bond formations between Csp^³-H bond adjacent to nitrogen and Csp^³-H bond of nitroalkanes are catalyzed efficiently by magnetically recoverable iron nanoparticles using oxygen. The catalyst can be magnetically removed and recycled easily for nine times without decreasing activity.

iron nanoparticles - oxygen - cross-coupling - C-C bond formation

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13

The leaching of Fe residue in the resulting crude material was detected by Thermo Jarrell Ash ICP-AES. No obvious Fe leaching was detected (below detecting limit).

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15

Experimental Procedure
Fe₃O₄ [<50 nm particle size (TEM)], Fe₂O₃ (<50 nm particle size) and other reagents were purchased from Sigma-Aldrich and used without further purification. 2-Aryl-1,2,3,4-tetrahydroisoquinolines were prepared by the literature method.^¹6 To a reaction tube charged with a magnetic stir bar and Fe₃O₄ nanoparticles (0.02 mmol, 10 mol%), 1,2,3,4-tetrahydroisoquinoline derivatives (0.2 mmol), and nitroalkane or acetone (0.5 mL) were added. Then the tube was filled up with molecular oxygen and stoppered. The reaction mixture was stirred at 100 ˚C (temperature of oil bath) for 24 h. The Fe₃O₄ nanoparticles were adsorbed on the magnetic stirring bar when the stirring was stopped. After cooled to r.t., the reaction solution was filtered through Celite in a pipette eluting with EtOAc. The volatile was removed in vacuo, and the residue was purified by column chromatography on silica gel (eluent: hexane-EtOAc = 5:1) to give the corresponding product. Fe₃O₄ nanoparticles were washed with EtOAc, air-dried, and used directly for the next round of reaction without further purification.
2-(3-Methoxyphenyl)-1,2,3,4-tetrahydroisoquinoline (1e) White solid. Isolated by flash column chromatography (hexane-EtOAc = 5:1, R _f  = 0.7). ^¹H NMR (400 MHz): δ = 7.26-7.15 (m, 5 H), 6.62-6.60 (m, 1 H), 6.53-6.52 (m, 1 H), 6.41-6.39 (m, 1 H), 4.42 (s, 2 H), 3.82 (s, 3 H), 3.57 (t, J = 5.6 Hz, 2 H), 2.99 (t, J = 6.0 Hz, 2 H) ppm. ^¹³C NMR (100 MHz): δ = 160.8, 151.9. 134.9, 134.5, 130.0, 128.5, 126.6, 126.4, 126.1, 108.0, 103.3, 101.5, 55.2, 50.6, 46.4, 29.2 ppm. HRMS (APCI): m/z calcd for C₁₆H₁₈NO [M + 1]⁺: 240.1383; found: 240.1381.
2-(3-Methoxyphenyl)-1-(nitromethyl)-1,2,3,4-tetrahydroisoquinoline (3i) Isolated by flash column chromatography (hexane-EtOAc = 5:1, R _f  = 0.4). Light yellow oil. ^¹H NMR (400 MHz): δ = 7.28-7.17 (m, 4 H), 7.14-7.12 (m, 1 H), 6.60 (dd, J = 8.4, 2.4 Hz, 1 H), 6.54 (m, 1 H), 6.42 (dd, J = 8.0, 2.0 Hz, 1 H), 5.54 (dd, J = 7.2, 6.8 Hz, 1 H), 4.87 (dd, J = 12.0, 7.2 Hz, 1 H), 4.55 (dd, J = 11.6, 6.8 Hz, 1 H), 3.80 (s, 3 H), 3.66-3.58 (m, 2 H), 3.00 (ddd, J = 16.4, 8.8, 6.4 Hz, 1 H), 2.68 (dt, J = 16.4, 5.2 Hz, 1 H) ppm. ^¹³C NMR (100 MHz): δ = 160.9, 149.7, 135.2, 132.9, 130.2, 129.2, 128.2, 127.0, 126.7, 107.5, 104.0, 101.4, 78.8, 58.3, 55.2, 42.1, 26.6 ppm. HRMS (APCI): m/z calcd for C₁₇H₁₉N₂O₃ [M + 1]⁺: 299.1390; found: 299.1391.
2-(3-Methoxyphenyl)-1-(1-nitroethyl)-1,2,3,4-tetrahydroisoquinoline (3j) The ratio of isolated diastereomers is 1.7. Isolated by flash column chromatography (hexane-EtOAc = 5:1, R _f  = 0.4). Light yellow oil.
Major isomer: ^¹H NMR (400 MHz): δ = 5.05 (dq, J = 14.8, 6.4 Hz, 1 H), 3.79 (s, 3 H), 1.55 (d, J = 6.4 Hz, 3 H) ppm. ^¹³C NMR (100 MHz): δ = 160.7, 150.2, 134.7, 131.9, 130.0, 128.7, 128.2, 126.6, 107.9, 104.0, 101.8, 85.4, 62.8, 55.2, 42.7, 26.5, 16.3 ppm.
Minor isomer: ^¹H NMR (400 MHz): δ = 4.88 (dq, J = 14.8, 6.4 Hz, 1 H), 3.82 (s, 3 H), 1.71 (d, J = 6.8 Hz, 3 H) ppm. ^¹³C NMR (100 MHz): δ = 160.8, 150.5, 135.6, 133.8, 130.1, 129.1, 128.3, 127.3, 107.2, 103.1, 101.1, 88.9, 61.2, 55.2, 43.5, 26.9, 17.5 ppm.
Other overlapped peaks: ^¹H NMR (400 MHz): δ = 7.27-7.08 (m), 7.01-7.00 (m), 6.62-6.52 (m), 6.40-6.37 (m), 5.25-5.24 (m), 3.85-3.83 (m), 3.58-3.52 (m), 3.52-3.04 (m), 2.96-2.86 (m) ppm. ^¹³C NMR (100 MHz): δ = 126.2 ppm. HRMS (APCI): m/z calcd for C₁₈H₂₁N₂O₃ [M + 1]⁺: 313.1547; found: 313.1549.
2-(3-Methoxyphenyl)-1-(1-nitropropyl)-1,2,3,4-tetrahydroisoquinoline (3k) The ratio of isolated diastereomers is 1.6. Isolated by flash column chromatography (hexane-EtOAc = 5:1, R _f  = 0.4). Light yellow oil.
Major isomer: ^¹H NMR (400 MHz): δ = 5.12 (d, J = 9.6 Hz, 1 H), 4.86 (m, 1 H), 3.77 (s, 3 H) ppm. ^¹³C NMR (100 MHz): δ = 160.5, 150.3, 135.5, 133.8, 130.1, 129.3, 128.5, 128.2, 125.9, 108.3, 103.9, 102.2, 92.9, 62.2, 55.2, 42.3, 25.8, 24.5 ppm.
Minor isomer: ^¹H NMR (400 MHz): δ = 5.22 (d, J = 9.2 Hz, 1 H), 4.67 (m, 1 H), 3.81 (s, 3 H) ppm. ^¹³C NMR (100 MHz): δ = 160.7, 150.3, 134.6, 132.1, 129.8, 128.6, 128.2, 127.2, 126.6, 106.8, 102.8, 100.8, 96.1, 60.7, 55.1, 43.5, 26.9, 25.0 ppm.
Other overlapped peaks: ^¹H NMR (400 MHz): δ = 7.26-7.08 (m), 7.01-7.18 (m), 7.00-6.98 (m), 6.62-6.52 (m), 6.40-6.35 (m), 3.87-3.47 (m), 3.12-3.06 (m), 2.93-2.85 (m), 2.26-2.06 (m), 1.86-1.78 (m), 0.96-0.92 (m) ppm. ^¹³C NMR (100 MHz): δ = 10.6 ppm. HRMS (APCI): m/z calcd for C₁₉H₂₃N₂O₃ [M + 1]⁺: 327.1703; found: 327.1703.

16 Kwong FY. Klapars A. Buchwald SL. Org. Lett.  2002,  4:  581