And also the ynamide (33.5 mg, 0.124 mmol) was performed at 30 for 18 h. The concentrated crude residue was purified by column chromatography (2:1 dichloromethane/hexanes) to provide 39.five mg (0.111 mmol, 90 ) of a white strong. 1H NMR (400 MHz): 7.56 (d, J = 7.9 Hz, 2H), 7.36-7.28 (m, 3H), 7.26 (d, J = eight.1 Hz, 2H), 7.21-7.13 (m, 2H), 2.40 (s, 3H), 1.19 (d, J = 1.3 Hz, 9H). 13C NMR (one hundred MHz): 193.0, 145.8, 137.four, 133.1, 129.eight, 129.three, 129.0, 128.1, 126.4, 89.2, 73.6, 44.6, 26.two, 21.6. Anal. Calcd For C20H21NO3S: C, 67.58; H, five.95; N, three.94. Discovered: C, 67.68; H, six.29; N, three.86. Mp 98-101 . N-(4-Methyl-3-oxopent-1-ynyl)-N-phenyl-4-tolylsulfonamide, 9. The reaction with isobutyryl chloride (30.4 mg, 0.28 mmol) and the ynamide (54.0 mg, 0.20 mmol) was performed at 15 for 52 h. The concentrated crude residue was purified by column chromatography (two:1 dichloromethane/hexanes) to offer 47.three mg (0.14 mmol, 70 ) of a colorless oil.1H NMR (400 MHz): 7.58 (d, J = 7.9 Hz, 2H), 7.40-7.26 (m, 5H), 7.23-7.14 (m, 2H), two.63 (hept, J = 7.1 Hz, 1H), two.42 (s, 3H), 1.84793-07-7 site 20 (d, J = 7.1 Hz, 6H). 13C NMR (one hundred MHz): 190.9, 145.9, 137.3, 132.9, 129.9, 129.4, 129.1, 128.1, 126.5, 89.1, 74.3, 42.7, 21.7, 18.1. Anal. Calcd For C19H19NO3S: C, 66.84; H, five.61; N, 4.ten. Located: C, 66.59; H, 5.86; N, four.00. N-Ethoxycarbonyl-1,2-dihydro-2-(N-phenyl-N-tosylaminoethynyl)pyridine, 10. The reaction amongst the ynamide (54.2 mg, 0.20 mmol) and pyridine (20 L, 0.24 mmol) was completed after 2.5 h. Chromatographic purification (1:7 Et2O/hexanes) gave 60.3 mg (0.14 mmol, 71 ) of a slightly yellow oil. 1H NMR (400 MHz): 7.42-7.72 (m, 2H), 7.21-7.33 (m, 5H), 7.14-7.21 (m, 2H), 6.76 (m, 1H), 5.99 (dd, J = 9.3, 5.six Hz, 1H), 5.43-5.82 (m, 2H), five.35 (d, J = 7.Ethyl 5-(2,5-dimethylphenoxy)pentanoate custom synthesis 3 Hz, 1H), four.PMID:34816786 18-4.34 (m, 2H), two.43 (s, 3H), 1.24-1.36 (m, 3H). 13C NMR (one hundred MHz): 153.eight, 153.0, 145.0, 144.eight, 138.7, 132.six, 129.four, 128.9, 128.five, 128.2, 128.1, 126.0, 125.1, 124.7, 122.5, 122.2, 118.four, 117.9, 105.two, 69.1, 62.six, 44.1, 43.5, 21.7, 14.five. Anal. Calcd for C23H22N2O4S: C, 65.38; H, 5.25; N, 6.63. Discovered: C, 65.17; H, five.36; N, six.51. N-Ethoxycarbonyl-1,2-dihydro-2-(N-phenyl-N-tosylaminoethynyl)-4-chloropyridine, 11. The ynamide (54.2 mg, 0.20 mmol), CuI (three.8 mg, 0.02 mmol), and N,N-diisopropylethylamine (70 L, 0.40 mmol) were dissolved in 1 mL of anhydrous dichloromethane. Then, a resolution of 4-bromopyridine hydrochloride (46.7 mg, 0.24 mmol), N,N-diisopropylethylamine (70 L, 0.40 mmol), and ethyl chloroformate (38 L, 0.40 mmol) in 1 mL of anhydrous dichloromethane was added. The reaction was completed following two.5 h. Chromatographic purification (3:eight Et2O/hexanes) gave 83.0 mg (0.18 mmol, 91 ) of a slightly yellow oil. 1H NMR (400 MHz): 7.54 (d, J = eight.0 Hz, 2H), 7.22-7.35 (m, 5H), 7.11-7.21 (m, 2H), 6.82 (m, 1H), five.71 (s, 1H), 5.56 (m, 1H), five.31 (dd, J = eight.0, two.1 Hz, 1H), four.19-4.34 (m, 2H), 2.44 (s, 3H), 1.27-1.34 (m, 3H). 13C NMR (100 MHz): 144.9, 138.five, 132.7, 129.4, 129.0, 128.4, 128.1, 126.6, 126.0, 113.six, 106.six, 78.5, 68.2, 63.0, 45.3, 21.six, 14.three. Anal. Calcd for C23H21ClN2O4S: C, 60.46; H, 4.63; N, 6.13. Identified: C, 60.28; H, four.90; N, six.13. N-Ethoxycarbonyl-1,2-dihydro-2-(N-phenyl-N-tosylaminoethynyl)-5-chloropyridine, 12. The reaction involving the ynamide (54.two mg, 0.20 mmol) and 3-chloropyridine (23 L, 0.24 mmol) was completed immediately after two.5 h. Chromatographic purification (1:7 Et2O/ hexanes) gave 67.1 mg (0.15 mmol, 73 ) of a slightly yellow oil. 1HNoteNMR (400 MHz): 7.44-7.59 (m, 2H), 7.22-7.33 (m, 5H), 7.14- 7.21 (m, 2H), six.77.