D at 500 and 125.eight MHz, respectively. HRMS data was obtained by ESI applying a TOF mass spectrometer. Basic procedure A for crosscoupling of (hetero)aryltrifluoroborates with 2chloroacetates and tertiary 2chloroacetamides An ovendried Biotage 10 mL microwave vial equipped having a magnetic stirbar was charged together with the (hetero)aryl trifluoroborate (0.525 mmol, 1.05 equiv), Cs2CO3 (1.five mmol, three equiv),J Org Chem. Author manuscript; offered in PMC 2014 April 19.Molander et al.Pageand XPhosPdG2 (3.93 mg, 5.0 mol, 1 mol ). A disposable Teflon septum cap was made use of to seal the vial, which was evacuated and purged with Ar 3 times. THF (1.6 mL), H2O (0.four mL), as well as the electrophile (0.five mmol, 1 equiv) were added by way of syringe with stirring beneath Ar. In instances exactly where the electrophile was a solid, it was added in conjunction with the solid supplies ahead of sealing the vial. The soln was heated at one hundred overnight. Following cooling to rt, the mixture was extracted with EtOAc (three mL), as well as the combined organic layers had been dried (Na2SO4). The crude solutions have been purified by flash column chromatography, eluting using a gradient of EtOAc in hexanes. Benzyl 2(3Methoxyphenyl)acetate (2a)General process A was employed. Column chromatography (hexanes/EtOAc = 9:1 to 1:3) offered 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), 6.92 (d, J =7.5 Hz, 1H), six.876.85 (m, 2H), five.12 (s, 2H), three.76 (s, 3H), three.63 (s, 2H). 13C NMR (125.8 MHz, CDCl3): 171.4, 159.9, 136.0, 135.four, 129.7, 128.7, 128.three, 128.3, 121.eight, 115.0, 113.0, 66.eight, 55.three, 41.five. IR (neat): 2919, 1736, 1490, 1261, 1147 cm1. HRMS (ESI) m/z calcd. For C16H17O3 (MH), 257.1178, found 257.1171. Benzyl two(2Methoxyphenyl)acetate (2b)Common procedure A was employed. Column chromatography (hexanes/EtOAc = 9:1 to 1:three) provided the title compound as a yellow oil in 66 yield (84 mg). 1H NMR (500 MHz, CDCl3): 7.387.34 (m, 5H), 7.297.26 (m, 1H), 7.227.20 (m, 1H), 6.956.93 (m, 1H), 6.876.86 (m, 1H), 5.16 (s, 2H), three.75 (s, 3H), 3.68 (s, 2H). 13C NMR (125.8 MHz, CDCl3): 171.9, 157.7, 136.4, 131.1, 128.eight, 128.7, 128.six, 128.two, 128.two, 123.1, 120.6, 110.five, 66.4, 55.five, 36.two. IR (neat): 2924, 1737, 1495, 1247, 1148 cm1. HRMS (ESI) m/z calcd. For C16H16O3Na (MNa) 279.0997, found 279.0997. Benzyl two(oTolyl)acetate (2c)General procedure A was employed. Column chromatography (hexanes/EtOAc = 9:1 to 1:3) offered 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 (125.8 MHz, CDCl3): 171.4, 137.0, 136.1, 132.8, 130.5, 130.3, 128.7, 128.3, 128.2, 127.6, 126.3, 66.7, 39.3, 19.7. IR (neat): 1734, 1498, 1455, 1257, 1146 cm1. HRMS (ESI) m/z calcd. For C16H16O2Na (MNa) 263.Methyl 6-formylnicotinate manufacturer 1048, discovered 263.2,3-Dibromo-4-methylpyridine structure 1048.PMID:24732841 Benzyl two(Quinolin6yl)acetate (2d)Basic procedure A was employed. Column chromatography (hexanes/EtOAc = 9:1 to 1:three) offered the title compound as a brown oil in 80 yield (111 mg). 1H NMR (500 MHz, CDCl3): eight.91 (br s, 1H), 8.128.07 (m, 2H), 7.72 (s, 1H), 7.697.67 (m, 1H), 7.437.42 (m, 1H), 7.377.34 (m, 5H), five.16 (s, 2H), three.86 (s, 2H). 13C NMR (125.8 MHz, CDCl3): 171.two, 150.4, 147.6, 136.0, 135.8, 132.five, 131.3, 129.9, 128.7, 128.5, 128.4, 128.1, 121.five, 67.0, 41.three. IR (neat): 2980, 1732, 1500, 1152 cm1. HRMS (ESI) m/z calcd. For C18H16NO2 (MH) 278.1181, located 278.1182. Benzyl two(two,3Dihydrobenzo[1,4]dioxin6yl)acetate (2e)19General process A was employed. Column chroma.