Phosphorus oxychloride → HCID 71470277, compound

Participants

Reaction Conditions

Reaction Steps

L-Boc-Lys(Boc)-OH (0.26 g, 0.75 mmol) was dissolved in 3 mL of pyridine. The solution was cooled to −25° C. and phosphorus oxychloride (0.12 g, 0.75 mmol) was added dropwise with vigorous stirring. After stirring for 15 min. at −25° C., 3-((perfluoropyridin-4-yl)ethynyl)aniline, (13b) (0.10 g, 0.36 mmol) in pyridine (3 mL) was added slowly. The reaction mixture was stirred for 0.5 h at −25° C. and then at room temperature for 10 h. The reaction mixture was quenched with ice/water and extracted with EtOAc. The organic layer was washed with sat. NaHSO4 three times, dried with Na SO4 and was concentrated in vacuo. The crude product was subjected to chromatography with CH2Cl2:CH3CN=1:30 and the product was obtained in 36% yield. (S)-Di-tert-butyl (6-oxo-6-((3-((perfluoropyridin-4-yl)ethynyl)phenyl)amino)hexane-1,5-diyl)dicarbamate (97 mg, 0.16 mmol) was dissolved in gaseous HCl saturated MeOH (4 mL) at 0° C. and the solution was stirred for 10 hours at room temperature. The solvent was evaporated and the product (65 mg, 86%) was purified by recrystallization with isopropanol: 1H-NMR (600 MHz, CD3OD) δ 8.07 (dd, J=1.74 Hz, J=1.68 Hz, 1H), 7.75 (ddd, J=7.98 Hz, J=1.92 Hz, J=1.14 Hz, 1H), 7.48 (dd, J=7.8 Hz, J=7.8 Hz, 1H), 7.43 (ddd, J=7.68 Hz, J=1.32 Hz, J=1.32 Hz, 1H) 4.12 (t, J=6.6 Hz, 1H), 2.97 (t, J=7.56 Hz, 2H), 2.00-2.07 (m, 1H), 1.97-2.00 (m, 1H), 1.74-1.77 (m, 2H), 1.56-1.60 (m, 2H); 13C-NMR (150 MHz, CD3OD) δ 168.7, 144.9 (dm, J=224 Hz), 143.5 (dm, J=262 Hz), 139.7, 130.8, 129.4, 124.2, 123.3, 122.4, 117.9 (m), 106.5 (m), 74.2 (m), 54.9, 40.3, 32.2, 28.2, 23.0; m.p. >250° C. (decomp.)

Provenance & Evidence