Enylfuran-3-yl)methyl 2-bromo-2,2-difluoroacetate (1q)–General Process A was followed utilizing (2-phenylfuran-3-yl)methanol17 (0.52 g, three.0 mmol). Workup provided the title compound as a yellow oil (0.93 g, 93 ). 1H NMR (400 MHz, CDCl3) 7.66 7.59 (m, two H), 7.51 7.45 (m, three H), 7.43 7.37 (m, 1 H), 6.61 (d, J = 1.9 Hz, 1 H), 5.40 (s, two H). 13C1H NMR (101 MHz, CDCl3) 159.7 (t, J = 31.six Hz), 153.four, 142.1, 129.9, 129.1, 128.7, 126.six, 113.56, 113.54, 108.eight (t, J = 314.6 Hz), 62.six. 19F NMR (376 MHz, CDCl3) -60.75 (s, two F). HRMS (EI): m/z [M]+ calcd for C13H9BrF2O3: 329.9703; found: 329.9701 (0.six ppm). IR (film): 3057, 2970, 1774, 1514, 1489, 1375, 1292, 11689, 1122, 1067, 943, 887, 842, 771, 736, 692, 660 cm-1. Dibenzo[b,d]thiophen-4-ylmethyl 2-bromo-2,2-difluoroacetate (1r)–General Process A was followed using dibenzo[b,d]thiophen-4-ylmethanol (1.2 g, five.6 mmol). Workup and chromatographic purification (hexanes) offered the title compound as a colorless strong (1.9 g, 89 ). mp 901 . 1H NMR (400 MHz, CDCl3) eight.22 eight.15 (m, two H), 7.94 7.86 (m, 1 H), 7.57 7.47 (m, four H), five.63 (s, 2 H). 13C1H NMR (101 MHz, CDCl3) 159.six (t, J = 31.7 Hz), 139.24, 139.15, 136.6, 135.4, 127.7, 127.37, 127.33, 124.90, 124.86, 123.0, 122.six, 122.0, 108.7 (t, J = 314.five Hz), 68.7. 19F NMR (376 MHz, CDCl3) -60.52 (s, 2 F). HRMS (APCI exane/PhMe): m/z [M]+ calcd for C15H9BrF2O2S: 369.9475; located: 369.9471 (1.1 ppm). IR (film): 3064, 2931, 1778, 1585, 1443, 1408, 1298, 1180, 1136, 1047, 982, 941, 883, 827, 789, 746, 710, 669 cm-1. (1-(Methylsulfonyl)-1H-indol-2-yl)methyl 2-bromo-2,2-difluoroacetate (1s)– Common Process A was followed using [1-(methylsulfonyl)-1H-indol-2-yl]methanol18 (1.1 g, 5.0 mmol). Workup and chromatographic purification (hexanes/EtOAc 1:09:1) offered the title compound as a grey solid (1.1 g, 70 ). mp 878 . 1H NMR (400 MHz, CDCl3) 8.05 (dt, J = eight.3, 1.0 Hz, 1 H), 7.66 7.61 (m, 1 H), 7.47 7.40 (m, 1 H), 7.38 7.Formula of 2-Iodo-1,3,5-trimethoxybenzene 31 (m, 1 H), 6.tert-Butyl 9-aminononanoate Chemical name 91 (s, 1 H), five.PMID:34816786 69 (s, 2 H), 3.19 (s, 3H). 13C1H NMR (101 MHz, CDCl3) 158.eight (t, J = 31.7 Hz), 137.two, 131.7, 128.three, 126.five, 124.three, 122.0, 114.eight, 114.1, 108.7 (t, J = 314.3 Hz), 62.7, 41.1. 19F NMR (376 MHz, CDCl3) -60.63 (s, two F). HRMS (APCIhexane/PhMe): m/z [M]+ calcd for C12H10BrF2NO4S: 380.9482; discovered: 380.9479 (0.eight ppm). IR (film): 3028, 1778, 1452, 1369, 1292, 1175, 1121, 964, 916, 823, 771, 748, 719, 685 cm-1. (5-(Furan-2-yl)-1-methyl-1H-pyrazol-3-yl)methyl 2-bromo-2,2-difluoroacetate (3a)–HO2CCF2Br (0.27 g, 1.five mmol) was added to a round-bottom flask, which was sealed having a rubber septum and attached to an oil bubbler. DCM (six.0 mL) and DMF (0.30 mL) have been injected, and also the answer was cooled to -10 . Oxalyl chloride (0.13 mL, 1.five mmol) was injected (caution: evolution of noxious gas), and following 5 min, the mixture was allowed to warm to rt. Immediately after two h, the mixture was cooled to 0 , plus a resolution of [5(furan-2-yl)-1-methyl-1H-pyrazol-3-yl]methanol13 (0.19 g, 1.0 mmol) and NEt3 (0.38 mL, two.7 mmol) in DCM (1.5 mL) was added. Right after 2.5 h, the reaction was quenched with water,Author Manuscript Author Manuscript Author Manuscript Author ManuscriptJ Org Chem. Author manuscript; accessible in PMC 2016 August 21.Ambler et al.Pageand the aqueous layer was extracted with EtOAc (four ten mL). The combined organic layers have been washed with brine, dried over Na2SO4, and filtered. Chromatographic purification (hexanes/EtOAc 1:03:two) provided the title compound as a yellow strong (0.29 g, 82 ). m.p. 390 . 1H NMR (400 MHz, CDCl3) 7.