217813-00-8

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the general procedure, treatment of quinoline (0.064 g, 59 μL, 0.50 mmol) and 4-chlorobenzaldehyde (0.105 g, 0.75 mmol) with 4,5-difluoro-2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.201 g, 0.60 mmol) in the presence of KF (0.070 g, 1.2 mmol) and 18-crown-6 (0.317 g, 1.2 mmol) in THF (2.0 mL) at −10° C. to room temperature for 12 hrs followed by flash column chromatography (Pet. ether/EtOAc=75/25) of the crude reaction mixture afforded 5-(4-chlorophenyl)-2,3-difluoro-5H,6aH-benzo[4,5][1,3]oxazino[3,2-a]quinoline as inseparable mixture of diastereomers as a white solid (0.118 g, 68% yield, dr determined by 1H NMR analysis of crude reaction mixture is 10:1). at −10° C. to room temperature for 12 hrs reaction mixture

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4,5-difluoro-2-(trimethylsilyl)phenyl trifluoromethanesulfonate (25 mg, 0.074 mmol), Cesium Fluoride (62 mg, 0.411 mmol), Trimethtyl phosphite (37 mg, 0.299 mmol), Acetonitrile (1 ml): Reaction Time: 4 h; Rf: 0.4 (1:3 EtOAc:Pet Ether); Thick oil; 11.8 mg, 71%; 1H NMR (400 MHz, CDCl3, TMS) δ 7.67-7.53 (m, 2H), 7.34-7.24 (m, 1H), 3.79 (s, 3H), 3.77 (s, 3H); 13C NMR (100 MHz, CDCl3, TMS) δ 153.3 (ddd, J=3.9, 12.3, 256.6 Hz), 150.3 (ddd, J=12.3, 22.4, 252.0 Hz), 129.0 (ddd, J=3.9, 6.9, 10.8 Hz), 124.2 (dt, J=3.9, 193.4 Hz), 121.3 (dd, J=11.6, J=18.5 Hz), 118.0 (t, J=17.7 Hz), 52.9 (d, J=6.2 Hz); 31P NMR (162 MHz, CDCl3) δ 18.6 (d, JPF=7.5 Hz); HRMS-ESI (m/z) calcd (C8H9F2O3P+H)+: 223.0330. found: 223.0335. 4 h

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4,5-difluoro-2-(trimethylsilyl)phenyl trifluoromethanesulfonate (25 mg, 0.078 mmol), Cesium Fluoride (62 mg, 0.411 mmol), Triethtyl phosphite (50 mg, 0.299 mmol), Acetonitrile (1 ml): Reaction Time 4 h; Rf: 0.5 (2:3 EtOAc:Pet Ether); Thick oil; 14.6 mg, 78%; 1H NMR (500 MHz, CDCl3, TMS) δ 7.67-7.55 (m, 2H), 7.31-7.23 (m, 1H), 4.21-4.05 (m, 4H), 1.34 (t, J=7.0 Hz, 6H); 13C NMR (125 MHz, CDCl3, TMS) δ 153.1 (ddd, J=3.8, 12.4, 255.6 Hz), 150.2 (ddd, J=13.4, 22.9, 252.7 Hz), 128.8 (ddd, J=3.8, 6.7, 10.5 Hz), 125.9 (dt, J=3.8, 192.7 Hz), 121.1 (dd, J=11.4, 18.1 Hz), 117.9 (t, J=18.1 Hz), 62.4 (d, J=4.8 Hz), 16.2 (d, J=5.7 Hz) 31P NMR (162 MHz, CDCl3) δ 15.8 (apparent t, JPF=6.1 Hz); HRMS-ESI (m/z) calcd (C10H13F2O3P+H)+: 251.0643. found: 251.0643.