Activation from the acidity 23 with CDI, and addition of the towards the pre-generated anion formed by deprotection of 9c with LiHMDS, produces the -keto ester 24 in 23% produce. 59%), which solidified upon chilling to 4?C. Books substance [16]. IR (CHCl3 Tauroursodeoxycholate solid): 3135, 1732, 1673, 1598, 1570, 1466, 1432?cm?1; 1H NMR (CDCl3, 500?MHz) 7.59 (dd, 1H, 8.57 (s, 1H, H2 or H6), 8.45 (s, 1H, H2 or H6), 7.81 (s, 1H, H4), 7.63 (m, 1H, H5), 7.28 (d, 1H, 184.1, 157.2, 151.1, 149.6, 148.7, 139.7, 135.5, 131.4, 129.3, 127.6, 126.2, 120.7, 120.4, 108.2, 41.7; HRMS (EI) calcd for C17H11BrClNO2 (M+), 374.9662; discovered: 376.9642. 2.14. 2-(5-Chloropyridin-3-yl)-2-fluoro-1-(furan-2-yl)ethanone (12a) To a remedy of 11a (20?mg, 0.09?mmol) in dry out THF (5?mL) was added LiHMDS (0.1?mL, 1.0?M solution in THF, 0.1?mmol) more than 5?min. The blend was stirred for 1?h in ?78?C. A remedy of NFSi (32?mg, 0.1?mmol) in dry out THF (3?mL) was added dropwise towards the blend more than 10?min. This is stirred for another 2?h in ?78?C. Saturated NaHCO3 (5?mL) was put into adjust the pH to 9, and the perfect solution is was extracted with EtOAc (3??15?mL). The mixed organic layers had been cleaned with brine (10?mL), dried more than MgSO4 and concentrated in vacuo. The merchandise was purified by column chromatography (50:50 EtOAc/hexanes) to produce 12a as a good (16?mg, 74%). IR (CHCl3 solid): 3136, 3059, 1690, 1584, 1569, 1464, 1425?cm?1. 1H NMR (CDCl3, 400?MHz) 8.67 (dd, 1H, 182.2 (d, 7.63 (dd, 1H, 183.2 (d, 181.8 (d, 181.2 (d, 175.8 (t, 7.71 (dd, 1H, 177.1 (t, 176.9 (t, 175.5 (t, 8.62 (d, 1H, 9.06 (s, 1H, Py9.05 (s, 1H, Py8.53 (d, 1H, 148.8, 148.2, 137.7, 137.2, 133.3, 42.5; HRMS (EI) calcd for C6H5Cl2N (M+), 160.9799; discovered: 160.9803. 2.26. (5-Chloropyridin-3-yl)acetonitrile (19) A remedy of 18 (0.10?g, 0.62?mmol) and KCN (0.10?g, 1.54?mmol) in dry out Tauroursodeoxycholate DMF (3?mL) was stirred for 48?h in 20?C. The solvent was eliminated in vacuo, as well as the residue was treated with K2CO3 option (15?mL, 10% w/w). The perfect solution is was after that extracted with EtOAc (3??15?mL). The mixed organic layers had been dried out over MgSO4 and focused in vacuo. The merchandise was purified by column chromatography (EtOAc) to produce 19 as a good (53?mg, 56%). IR (CHCl3 solid): 3048, 3031, 2928, 2251, 2231, 1583, 1566, 1447, 1413?cm?1; 1H NMR (CDCl3, 400?MHz) 8.57 (d, 1H, 148.5, 146.7, 135.2, 132.4, 127.2, 116.1, 20.7; HRMS (EI) calcd for C7H5ClN2 (M+), 152.0141; discovered: 152.0138. 2.27. Ethyl 3-diazo-2-oxopropanoate(21) This is prepared by changes of the books treatment [20]. To a remedy of ethyl chloro-oxoacetate (1.6?mL, 14?mmol) in THF (20?mL) was added dropwise TMSCHN2 (21?mL, 2?M solution in hexane, 42?mmol). After 3?h of stirring in 20?C, the solvent was removed in vacuo and the merchandise was purified by column chromatography about silica gel (25:75 EtOAc/hexanes) to produce 21 as a good (1.35?g, 68%). IR (CHCl3 solid): 3458, 3241, 3080, 2994, 2971, 2943, 2909, 2869, 2432, 2159, 2109, 1734, 1697, 1641, 1530, 1476, 1459, 1442?cm?1; 1H NMR (CDCl3, 400?MHz) 6.15 (s, 1H, COC8.08 (d, 2H, 8.07 (d, 2H, 164.1, 161.3, 145.8, 138.9, 135.2, 130.5, 129.6, 126.5; HRMS (EI) calcd for C10H6ClNO3 (M+), 223.0036; discovered: 223.0040. 2.30. Methyl 2-(5-bromopyridin-3-yl)-3-(2-(4-chlorophenyl)oxazol-5-yl)-3-oxopropanoate(24) This is from 23 (112?mg, 0.5?mmol) following a treatment described for 10a. Purification by adobe flash chromatography on silica gel (25:75 EtOAc/hexanes) afforded 24 as a good (50?mg, 23%). (Combination of enol isomer A and keto isomer B, 3:2 percentage). IR (CHCl3 solid): 2954, 1744, 1683, 1650, 1603, 1580, 1556, 1526, 1473, 1443, 1408?cm?1; 1H NMR (CDCl3, 300?MHz) (isomer A) 8.75 (d, 1H, 8.68 (d, 1H, 8.65-8.61 (m, 1H, H2 or H6), 8.52C8.48 (m, 1H, H2 or H6), 8.10 (d, 2H, 183.3, 163.8, 149.9, 148.7, 148.5, 139.6, 138.5, 136.0, 130.3, 129.4, 128.6, 124.3, 120.7, 42.3; HRMS (EI) calcd for C16H10BrClN2O2 (M+), 377.9594; discovered: 377.9608. 2.32. Methyl 2-(5-bromopyridin-3-yl)-3-(5-(4-chlorophenyl)isoxazol-3-yl)-3- oxopropanoate (27) This.IR (CHCl3 solid): 3136, 3059, 1690, 1584, 1569, 1464, 1425?cm?1. 2-(3-Chlorophenyl)-1-(furan-2-yl)ethanone (11b) This is from 10b (160?mg, 0.58?mmol) following a process of 11a. Purification by adobe flash chromatography on silica gel (25:75 EtOAc/hexanes) afforded 11b as an essential oil (75?mg, 59%), which solidified upon chilling to 4?C. Books substance [16]. IR (CHCl3 solid): 3135, 1732, 1673, 1598, 1570, 1466, 1432?cm?1; 1H NMR (CDCl3, 500?MHz) 7.59 (dd, 1H, 8.57 (s, 1H, H2 or H6), 8.45 (s, 1H, H2 or H6), 7.81 (s, 1H, H4), 7.63 (m, 1H, H5), 7.28 (d, 1H, 184.1, 157.2, 151.1, 149.6, 148.7, 139.7, 135.5, 131.4, 129.3, 127.6, 126.2, 120.7, 120.4, 108.2, 41.7; HRMS (EI) calcd for C17H11BrClNO2 (M+), 374.9662; discovered: 376.9642. 2.14. 2-(5-Chloropyridin-3-yl)-2-fluoro-1-(furan-2-yl)ethanone (12a) To a remedy of 11a (20?mg, 0.09?mmol) in dry out THF (5?mL) was added LiHMDS (0.1?mL, 1.0?M solution in THF, 0.1?mmol) more than 5?min. The blend was stirred for 1?h in ?78?C. A remedy of NFSi (32?mg, 0.1?mmol) in dry out THF (3?mL) was added dropwise towards the blend more than 10?min. This is stirred for another 2?h in ?78?C. Saturated NaHCO3 (5?mL) was put into adjust the pH to 9, and the perfect solution is was extracted with EtOAc (3??15?mL). The mixed organic layers had been cleaned with brine (10?mL), dried more than MgSO4 and concentrated in vacuo. The merchandise was purified by column chromatography (50:50 EtOAc/hexanes) to produce 12a as a good (16?mg, 74%). IR (CHCl3 solid): 3136, 3059, 1690, 1584, 1569, 1464, 1425?cm?1. 1H NMR (CDCl3, 400?MHz) 8.67 (dd, 1H, 182.2 (d, 7.63 (dd, 1H, 183.2 (d, 181.8 (d, 181.2 (d, 175.8 (t, 7.71 (dd, 1H, 177.1 (t, 176.9 (t, 175.5 (t, 8.62 (d, 1H, 9.06 (s, 1H, Py9.05 (s, 1H, Py8.53 Tauroursodeoxycholate (d, 1H, 148.8, 148.2, 137.7, 137.2, 133.3, 42.5; HRMS (EI) calcd for C6H5Cl2N (M+), 160.9799; discovered: 160.9803. 2.26. (5-Chloropyridin-3-yl)acetonitrile (19) A remedy of 18 (0.10?g, 0.62?mmol) and KCN (0.10?g, 1.54?mmol) in dry out DMF (3?mL) was stirred for 48?h in 20?C. The solvent was eliminated in vacuo, as well as the residue was treated with K2CO3 option (15?mL, 10% w/w). The perfect solution is was after that extracted with EtOAc (3??15?mL). The mixed organic layers had been dried out over MgSO4 and focused in vacuo. The merchandise was purified by column chromatography (EtOAc) to produce 19 as a good (53?mg, 56%). IR (CHCl3 solid): 3048, 3031, 2928, 2251, 2231, 1583, 1566, 1447, 1413?cm?1; 1H NMR (CDCl3, 400?MHz) 8.57 (d, 1H, 148.5, 146.7, 135.2, 132.4, 127.2, 116.1, 20.7; HRMS (EI) calcd SERPINA3 for C7H5ClN2 (M+), 152.0141; discovered: 152.0138. 2.27. Ethyl 3-diazo-2-oxopropanoate(21) This is prepared by changes of the books treatment [20]. To a remedy of ethyl chloro-oxoacetate (1.6?mL, 14?mmol) in THF (20?mL) was added dropwise TMSCHN2 (21?mL, 2?M solution in hexane, 42?mmol). After 3?h of stirring in 20?C, the solvent was removed in vacuo and the merchandise was purified by column chromatography about silica gel (25:75 EtOAc/hexanes) to produce 21 as a good (1.35?g, 68%). IR (CHCl3 solid): 3458, 3241, 3080, 2994, 2971, 2943, 2909, 2869, 2432, 2159, 2109, 1734, 1697, 1641, 1530, 1476, 1459, 1442?cm?1; 1H NMR (CDCl3, 400?MHz) 6.15 (s, 1H, COC8.08 (d, 2H, 8.07 (d, 2H, 164.1, 161.3, 145.8, 138.9, 135.2, 130.5, 129.6, 126.5; HRMS (EI) calcd for C10H6ClNO3 (M+), 223.0036; discovered: 223.0040. 2.30. Methyl 2-(5-bromopyridin-3-yl)-3-(2-(4-chlorophenyl)oxazol-5-yl)-3-oxopropanoate(24) This is from 23 (112?mg, 0.5?mmol) following a treatment described for 10a. Purification by adobe flash chromatography on silica gel (25:75 EtOAc/hexanes) afforded 24 as a good (50?mg, 23%). (Combination of enol isomer A and keto isomer B, 3:2 percentage). IR (CHCl3 solid): 2954, 1744, 1683, 1650, 1603, 1580,.