Synthesis of new N/S-containing compounds by Pd-catalyzed tandem reactions

References

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• Experimental procedure: In a microwave vial were added a solution of sulfide 1a or 1q (1 equiv), Pd(PPh3)4 (0.1 equiv), Na2CO3 (3.0 equiv), tetrabutylammonium iodide (0,25 equiv), and phenyl boronic acid (1.5 equiv) in a mixture (4:1) of 1,4-dioxane and water. The vial was sealed, and the mixture was irradiated for 3 hours at 130 °C. The reaction mixture was then evaporated, heptane was added to dissolve the product, then the solution was filtered, and then concentrated under reduced pressure. The crude mixture was analyzed by 1H-NMR and then purified by flash column chromatography on silica gel to afford 7r (from 1a) or 7q (from 1q). 7r: 1H-NMR (CDCl3): δ 7.64 (d, J = 7.9 Hz, 1H), 7.40 (d, J= 7.9 Hz, 1H), 7.32 – 7.28 (m, 2H), 7.21 (t, J = 7.4 Hz, 1H), 7.14 – 7.04 (m, 3H), 7.03 (d, J = 7.5 Hz, 2H), 6.90 (t, J = 7.4 Hz, 1H), 6.73 (t, J = 7.5 Hz, 1H), 6.65 (d, J = 7.7 Hz, 1H), 5.60 (d, J = 15.8 Hz, 1H), 5.12 (d, J = 15.8 Hz, 1H), 4.69 (d, J = 14.9 Hz, 1H), 4.58 (d, J = 14.8 Hz, 1H), 2.68 – 2.59 (m, 1H), 2.56 – 2.47 (m, 1H), 0.56 (t, J = 7.4 Hz, 3H),. 13C-NMR (100 MHz): 151.3, 146.2, 142.2, 141.5, 135.6, 133.0, 132.9, 132.7, 130.8, 128.9, 128.1, 127.5, 127.3, 126.9, 122.9, 122.3, 119.9, 108.8, 45.5, 31.0, 28.1, 11.6. HRMS m/z calcd for C25H23N2S [M + H]+: 383.1582, found: 383.1573. 7q: 1H-NMR (CDCl3): δ 7.50 (d, J = 7.8 Hz, 1H), 7.20 (t, J = 7.5 Hz, 1H), 7.16 – 7.12 (m, 2H), 7.12 - 7.04 (m, 4H), 6.95 – 6.91 (m, 2H), 6.85 (td, J = 7.5, 1.4, 1H), 6.51 (td, J = 7.6, 1.3, 1H), 6.33 (dd, J = 7.7, 1.4, 1H), 5.57 (d, J = 17.7 Hz, 1H), 5.42 (d, J = 17.7 Hz, 1H), 4.66 (d, J = 12.3 Hz, 1H), 4.06 (d, J = 12.4 Hz, 1H), 2.90 – 2.83 (m, 1H), 2.73 – 2.65 (m, 1H), 1.11 (t, J = 7.2 Hz, 3H).
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• Reviews on the desulfanylative coupling:
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• Experimental procedure: To a sealed tube containing a mixture of substrates 12a (0.5 equiv) and 12b (0.5 equiv), phenyl boronic acid (3.0 equiv), K2CO3 (3.0 equiv), Pd2(dba)3 (5 mol%) and PCy3 (20 mol%), was added as the solvent a mixture of 1,4-dioxane/water (4:1, 0.1 M). This mixture was deoxygenated using a freeze-thaw method (three cycles), put under argon atmosphere, and sealed, then stirred at 130 °C for 19 h. The resulting reaction mixture was concentrated to dryness under reduced pressure and the crude residue was purified by flash column chromatography on silica gel to afford a mixture of products 13a8 and 13b in a 1:1 ratio. 13b: 1H NMR (400 MHz, CDCl3) δ 7.51 – 7.44 (m, 2H), 7.40 – 7.33 (m, 2H), 7.26 (m, 6H), 7.17 – 7.09 (m, 2H), 7.06 – 6.99 (m, 2H), 6.99 – 6.93 (m, 3H), 6.93 – 6.87 (m, 2H), 4.83 (t, J = 6.2 Hz, 1H), 4.32 (d, J = 6.2 Hz, 2H), 3.51 (s, 2H), 2.10 (s, 3H), 1.54 (q, J = 7.5 Hz, 2H), 0.59 (t, J = 7.5 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 147.7, 140.9, 137.9, 137.0, 134.7, 133.4, 131.4, 131.4, 131.3, 129.9, 129.4, 129.3, 129.1, 129.0, 128.8, 128.7, 128.7, 128.2, 126.9, 126.4, 118.0, 77.5, 77.2, 76.8, 43.4, 35.8, 25.3, 21.2, 13.2. HRMS (ESI-Q-TOF) m/z calcd for C34H32N2S [M]+: 500.2286, found: 500.2299.
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