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Synlett 2015; 26(09): 1253-1257
DOI: 10.1055/s-0034-1379911
DOI: 10.1055/s-0034-1379911
letter
Palladium-Catalyzed Heck-Type Coupling via C–N Cleavage
Weitere Informationen
Publikationsverlauf
Received: 02. Februar 2015
Accepted after revision: 17. März 2015
Publikationsdatum:
02. April 2015 (online)
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Abstract
A palladium-catalyzed Heck-type coupling method between arenes and ketone Mannich bases via C–N cleavage to synthesize chalcones is reported. This protocol offers good yields and tolerates a broad range of functional groups. Based on the extensive experimental data, we propose a plausible coulping mechanism.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1379911.
- Supporting Information
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References and Notes
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- 18 Synthesis of 3a–p A mixture of 1 (0.2 mmol), 2 (0.6 mmol), DMSO (3 mL), Pd(OAc)2 (5 mol%), and Ag2CO3 and Ag2O (1.5 equiv, 1:1) was stirred at 120 °C under air atmosphere for 24 h. To the reaction mixture was added H2O and EtOAc, and the aqueous phase was extracted with EtOAc (3×). The combined organic layer was washed with brine, dried over Na2SO4, and evaporated under reduced pressure. The crude product was purified by silica gel column chromatography to give the corresponding products (3a,12 3g,13 3h,14 3i–l,9 3m,16 3n,17 3p,q,s–v 9 according to the literature). (E)-3-(2,3,4,6-Tetrafluorophenyl)-1-phenylprop-2-en-1-one (3b) Yield 74%. 1H NMR (500 MHz, CDCl3): δ = 7.85 (d, J = 7.2 Hz, 2 H), 7.78–7.50 (m, 4 H), 7.35 (d, J = 16.8 Hz, 1 H), 7.08 (m, 1 H). 13C NMR (125 MHz, CDCl3): δ = 190.2, 153.0 (dm, J = 248.0 Hz), 149.9 (dm, J = 251.0 Hz), 148.5 (dm, J = 249.6 Hz), 139.2 (dm, J = 241.2 Hz), 136.8, 135.9 (m), 131.5, 128.6, 126,9, 115.8, 114.1 (m), 102.9 (m). 19F NMR (282 MHz, CDCl3): δ = –118.5 (t, J = 9.6 Hz, 1 F), –134.9 (m, 1 F), –138.7 (dd, J = 19.5, 5.5 Hz, 1 F), –163.8 (m, 1 F). HRMS: m/z calcd for C15H8OF4: 280.0511; found: 280.0517. (E)-3-(2,4,6-Trifluorophenyl)-1-phenylprop-2-en-1-one (3c) Yield 71%. 1H NMR (500 MHz, CDCl3): δ = 7.84 (d, J = 7.0 Hz, 2 H), 7.62–7.50 (m, 4 H), 7.34 (d, J = 16.6 Hz, 1 H), 6.96 (t, J = 9.0 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 189.8, 165.2 (dm, J = 248.8 Hz), 139.1, 135.8 (m), 130.5, 128.9, 127.8, 117.1, 111.9 (m), 101.9 (m). 19F NMR (282 MHz, CDCl3): δ = –105.7 (m, 1 F), –113.1 (t, J = 8.2 Hz, 2 F). HRMS: m/z calcd for C15H9OF3: 262.0605; found: 262.0613. (E)-3-(2,3,5,6-Tetrafluorophenyl)-1-phenylprop-2-en-1-one (3d) Yield 79%. 1H NMR (500 MHz, CDCl3): δ = 7.837–7.75 (m, 3 H), 7.68–7.59 (m, 3 H), 7.35 (d, J = 17.4 Hz, 1 H), 7.15 (m, 1 H). 13C NMR (125 MHz, CDCl3): δ = 190.3, 149.5 (dm, J = 256.4 Hz), 145.8 (dm, J = 262.5 Hz), 138.7 (m), 137.1, 128.5, 127.6, 118.3 (m), 114.5, 103.6 (t, J = 22.8 Hz). 19F NMR (282 MHz, CDCl3): δ = –139.7 (m, 2 F), –144.8 (m, 2 F). HRMS: m/z calcd for C15H8OF4: 280.0511; found: 280.0508. (E)-3-(4-Cyano-2,3,5,6-tetrafluorophenyl)-1-phenylprop-2-en-1-one (3e) Yield 77%. 1H NMR (500 MHz, CDCl3): δ = 8.04–8.02 (m, 2 H), 7.98 (d, J = 16.0 Hz, 1 H), 7.78 (d, J = 16.0 Hz, 1 H), 7.67–7.55 (m, 3 H). 13C NMR (125 MHz, CDCl3): δ = 188.9, 148.5 (dm, J = 246.3 Hz), 145.3 (dm, J = 257.9 Hz), 138.5 (m), 135.4, 129.9, 128.3, 128.4, 127.5, 116.1 (t, J = 13.7 Hz), 114.7, 99.3 (m). 19F NMR (282 MHz, CDCl3): δ = –132.5 (dd, J = 21.6, 8.0 Hz, 2 F), –138.4 (dd, J = 21.6, 8.2 Hz, 2 F). HRMS: m/z calcd for C16H7ONF4: 305.0464; found: 305.0471. (E)-3-(5-Methyl-2-thienyl)-1-(4-nitrophenyl)-2-propen-1-one (3r) Yield 79%. 1H NMR (500 MHz, CDCl3): δ = 8.14 (d, J = 8.0 Hz, 2 H), 7.95 (d, J = 15.4 Hz, 1 H), 7.68 (d, J = 8.0 Hz, 2 H), 7.34 (d, J = 3.6 Hz, 1 H), 7.25 (d, J = 15.4 Hz, 1 H), 6.88 (d, J = 3.6 Hz, 1 H), 2.62 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 189.8, 146.8, 140.2, 140.0, 139.3, 137.5, 134.2, 129.9, 128.5, 127.3, 118.4, 16.1. HRMS: m/z calcd for C14H11NO3S: 273.0460; found: 273.0465.
For selected examples of the syntheses of organic functional materials from chalcones, see:
For selected books and reviews, see:
For the reactions that involve dehydrogenation to olefins followed by a coupling process, see: