D at 500 and 125.eight MHz, respectively. HRMS data was obtained by ESI working with a TOF mass spectrometer. Basic process A for crosscoupling of (hetero)aryltrifluoroborates with 2chloroacetates and tertiary 2chloroacetamides An ovendried Biotage ten mL microwave vial equipped having a magnetic stirbar was charged with all the (hetero)aryl trifluoroborate (0.525 mmol, 1.05 equiv), Cs2CO3 (1.5 mmol, three equiv),J Org Chem. Author manuscript; offered in PMC 2014 April 19.Molander et al.Pageand XPhosPdG2 (three.93 mg, 5.0 mol, 1 mol ). A disposable Teflon septum cap was used to seal the vial, which was evacuated and purged with Ar 3 occasions. THF (1.6 mL), H2O (0.4 mL), as well as the electrophile (0.five mmol, 1 equiv) had been added by way of syringe with stirring under Ar. In cases where the electrophile was a solid, it was added in addition to the strong supplies before sealing the vial. The soln was heated at 100 overnight. Immediately after cooling to rt, the mixture was extracted with EtOAc (3 mL), and the combined organic layers have been dried (Na2SO4). The crude items have been purified by flash column chromatography, eluting with a gradient of EtOAc in hexanes.896464-16-7 custom synthesis Benzyl two(3Methoxyphenyl)acetate (2a)General process A was employed. Column chromatography (hexanes/EtOAc = 9:1 to 1:3) provided the title compound as a yellow oil in 80 yield (102 mg). 1H NMR (500 MHz, CDCl3): 7.337.30 (m, 5H), 7.247.22 (m, 1H), six.92 (d, J =7.five Hz, 1H), six.876.85 (m, 2H), five.12 (s, 2H), 3.76 (s, 3H), three.63 (s, 2H). 13C NMR (125.eight MHz, CDCl3): 171.four, 159.9, 136.0, 135.4, 129.7, 128.7, 128.3, 128.3, 121.eight, 115.0, 113.0, 66.eight, 55.3, 41.5. IR (neat): 2919, 1736, 1490, 1261, 1147 cm1. HRMS (ESI) m/z calcd. For C16H17O3 (MH), 257.1178, identified 257.1171. Benzyl 2(2Methoxyphenyl)acetate (2b)Basic procedure A was employed. Column chromatography (hexanes/EtOAc = 9:1 to 1:3) supplied the title compound as a yellow oil in 66 yield (84 mg). 1H NMR (500 MHz, CDCl3): 7.5-Bromo-1-cyclopropyl-1H-pyrazole site 387.PMID:33636220 34 (m, 5H), 7.297.26 (m, 1H), 7.227.20 (m, 1H), six.956.93 (m, 1H), 6.876.86 (m, 1H), 5.16 (s, 2H), 3.75 (s, 3H), three.68 (s, 2H). 13C NMR (125.8 MHz, CDCl3): 171.9, 157.7, 136.four, 131.1, 128.8, 128.7, 128.six, 128.2, 128.2, 123.1, 120.six, 110.5, 66.four, 55.five, 36.2. IR (neat): 2924, 1737, 1495, 1247, 1148 cm1. HRMS (ESI) m/z calcd. For C16H16O3Na (MNa) 279.0997, discovered 279.0997. Benzyl two(oTolyl)acetate (2c)Common procedure A was employed. Column chromatography (hexanes/EtOAc = 9:1 to 1:3) provided the title compound as a light yellow oil in 87 yield (104 mg). 1H NMR (500 MHz, CDCl3): 7.317.29 (m, 5H), 7.187.16 (m, 4H), five.12 (s, 2H), 3.67 (s, 2H), two.28 (s, 3H). 13C NMR (125.eight MHz, CDCl3): 171.4, 137.0, 136.1, 132.8, 130.five, 130.three, 128.7, 128.3, 128.two, 127.six, 126.three, 66.7, 39.three, 19.7. IR (neat): 1734, 1498, 1455, 1257, 1146 cm1. HRMS (ESI) m/z calcd. For C16H16O2Na (MNa) 263.1048, identified 263.1048. Benzyl 2(Quinolin6yl)acetate (2d)Common procedure A was employed. Column chromatography (hexanes/EtOAc = 9:1 to 1:3) provided the title compound as a brown oil in 80 yield (111 mg). 1H NMR (500 MHz, CDCl3): 8.91 (br s, 1H), eight.128.07 (m, 2H), 7.72 (s, 1H), 7.697.67 (m, 1H), 7.437.42 (m, 1H), 7.377.34 (m, 5H), 5.16 (s, 2H), 3.86 (s, 2H). 13C NMR (125.8 MHz, CDCl3): 171.two, 150.four, 147.6, 136.0, 135.8, 132.five, 131.three, 129.9, 128.7, 128.five, 128.four, 128.1, 121.5, 67.0, 41.three. IR (neat): 2980, 1732, 1500, 1152 cm1. HRMS (ESI) m/z calcd. For C18H16NO2 (MH) 278.1181, identified 278.1182. Benzyl two(two,3Dihydrobenzo[1,4]dioxin6yl)acetate (2e)19General procedure A was employed. Column chroma.
