SUCCESS2016-08-10T22:58:56.93500991a34bdb-ba93-4833-b344-91857404f3f2ClC=1C=CC(=NC1C1=CC=CC=C1)C(=O)OC(C)C1isopropyl 5-chloro-6-phenylpicolinateFC=1C=CC(=NC1C1=CC=CC=C1)C(=O)OC(C)C2Isopropyl 5-Fluoro-6-phenylpicolinateproduct3acompounds[N+](=O)([O-])C1=C(C#N)C=CC=C13d2-Nitrobenzonitrile2-nitrobenzonitrileFC1=C(C#N)C=CC=C142-FluorobenzonitrileproductFC(S(=O)(=O)OC1=NC=CC=C1)(F)F5ePyridin-2-yl trifluoromethanesulfonateFC=1C=CC(=NC1C1=CC=C(C=C1)Cl)C(=O)OC(C)C°C73–767Isopropyl 5-Fluoro-6-(p-chlorophenyl)picolinateproductFC=1C=CC(=NC1C1=CC=C(C=C1)OC)C(=O)OC(C)C°C46–488Isopropyl 5-Fluoro-6-(p-methoxyphenyl)picolinateproductFC1=CC(=NC(=C1F)C1=CC=CC=C1)C(=O)OC(C)C9Isopropyl 4,5-Difluoro-6-phenylpicolinateFC1=CC(=NC(=C1F)C1=CC=C(C=C1)Cl)C(=O)OC(C)C°C74–7610Isopropyl 4,5-Difluoro-6-(p-chlorophenyl)picolinateproductFC1=CC(=NC(=C1F)C1=CC=C(C=C1)OC)C(=O)OC(C)C°C37–3811Isopropyl 4,5-Difluoro-6-(p-methoxyphenyl)picolinateproductFC1=NC2=CC=CC=C2C=C1122-FluoroquinolineFC1=CC=NC2=CC(=CC=C12)C(F)(F)F°C84–86134-Fluoro-7-(trifluoromethyl)quinolineproductFC1=NC=CC2=CC=CC=C12141-FluoroisoquinolineC(C1=CC=CC=C1)OC=1C=CC=C2C=CC(=NC12)F°C67–69CDCl3125.7513C161.5Hz242d153.4142.0Hz9.5d138.7137.6Hz15.3d136.8128.6128.0Hz1.9d127.0126.9126.1Hz2.9d119.6111.6110.6Hz42.9d70.7MHzproduct158-(benzyloxy)-2-fluoroquinoline8-(Benzyloxy)-2-fluoroquinolineFC=1N=NC(=CC1)C1=CC=CC=C1cm–11584cm–11556cm–11450cm–11427cm–11278cm–11108cm–1852cm–1778cm–1739CDCl310019F–84.8Hz1.5dMHzCDCl35001H8.01–7.983Hmultiple peaks7.53–7.493Hmultiple peaks7.29Hzdd1H9.5 , 2.0MHzCDCl3175.9513C166.7Hz245d159.2Hz3.5d135.1Hz2.1d130.2129.5Hz7.6d129.0127.0116.1Hz33.4dMHz16°C129–1313-Fluoro-6-phenylpyridazineFC1=NC=CC=C1C(F)(F)F172-Fluoro-3-(trifluoromethyl)pyridineFC1=NC=C(C=C1)C(F)(F)F182-Fluoro-5-(trifluoromethyl)pyridineFC1=NC=CC(=C1)C#N192-Fluoro-4-cyanopyridineFC1=NC=CC=C1C#N202-Fluoro-3-cyanopyridineFC1=NC=C(C=C1)C#N212-Fluoro-5-cyanopyridineFC1=NC=CN=C1222-FluoropyrazineFC1=NC=CC=C1Cl232-Fluoro-3-chloropyridineFC1=NC=C(C=C1)I242-Fluoro-5-iodopyridineFC1=NC=C(C=C1)[N+](=O)[O-]252-Fluoro-5-nitropyridineFC1=NC=C(C=C1)Br262-Fluoro-5-bromopyridineFC1=NC(=CC=C1)F272,6-DifluoropyridineFC=1C=C(C#N)C=CC1283-fluorobenzonitrile3-FluorobenzonitrileproductFC1=CC=C(C#N)C=C1294-FluorobenzonitrileFC1=CC=C(C(=O)OCC)C=C130Ethyl 4-FluorobenzoateFC1=CC=C(C(=O)C2=CC=CC=C2)C=C1°C47–48314-FluorobenzophenoneNHCsN - heterocyclic carbenesN-heterocyclic carbenes[C-]#N.C(CCC)[N+](CCCC)(CCCC)CCCCtetrabutylammonium cyanideTBACNalkali metal fluoridesMF[F-]fluorideFluoride[F-].C[N+](C)(C)Ctetramethylammonium fluorideTetramethylammonium Fluoridepp 12137–12145aryl-FarenesFluorinated arenesheteroarenes[H]*hydrogenCFC–Fheteroaryl fluorides(hetero)aryl halideDiMagno[F-].C(CCC)[N+](CCCC)(CCCC)CCCCtetrabutylammonium fluorideFC1=C(C(=C(C(=C1F)F)F)F)FhexafluorobenzeneCl*chloro-fluoridesacyl azolium fluoridesNMe4ClNMe4OHfluoroarenephenolsaryl fluorideschloropicolinates(hetero)aromaticClC=1C=CC(=NC1)C(=O)[O-]5-chloropicolinateFC=1C(=NC=CC1)C(=O)[O-]fluoropicolinatecarboxylic acid2-CO2Hisopropyl ether 1-iPrOCFCH3Facyl azolium fluorideNMe4F·4H2OOH2OF[H-]FBifluorideCH2Cl22-substituted-benzonitrile substratesaryl iodidesN(=O)[O-]nitrite2-chloro2-bromo2-iodoFC1=NC=CC=C12-fluoropyridineproduct(hetero)aryl triflates[O-]S(=O)(=O)C(F)(F)FtriflateBrC1=NC=CC=C12-bromopyridine2-halopyridinesmonochloropicolinatesdichloropicolinatesClC1=C(C(=NC=C1)C(=O)[O-])Cldichloropicolinate[Cl-]chlorideChloroquinoline, chloroisoquinolineClC=1N=NC=CC1chloropyridazineMethoxy, cyanoFC(F)(F)*trifluoromethyl2- and 4-fluorobenzonitrileClC1=CC=C(C(=O)OCC)C=C1ethyl 4-chlorobenzoateClC1=CC=C(C(=O)C2=CC=CC=C2)C=C14-chlorobenzophenone3–10-fold1H and 13C1H δc1ccc(cc1)c2ccccc2diphenyldimethyl polysiloxane[He]HeliumCN(C=O)CN,N-dimethylformamideIsopropyl chloroarylpicolinates2-Cyanophenyl trifluoromethanesulfonate, pyridine-2-yl trifluoromethanesulfonateP2O5N#NN2S(=O)(=O)([O-])[O-].[Mg+2]magnesium sulfateO=[Si]=Osilica gelC(C)OCCdiethyl etherC15H15FNO2[N]nitrogenO=[Si]=OSilicaClC=1C=CC(=NC1C1=CC=C(C=C1)Cl)C(=O)OC(C)Cisopropyl 5-chloro-6-(p-chlorophenyl)picolinateC15H14ClFNO2ClC=1C=CC(=NC1C1=CC=C(C=C1)OC)C(=O)OC(C)Cisopropyl 5-chloro-6-(p-methoxyphenyl)picolinateC16H17FNO3ClC1=CC(=NC(=C1Cl)C1=CC=CC=C1)C(=O)OC(C)Cisopropyl 4,5-dichloro-6-phenylpicolinateC15H14F2NO2ClC1=CC(=NC(=C1Cl)C1=CC=C(C=C1)Cl)C(=O)OC(C)Cisopropyl 4,5-dichloro-6-(p-chlorophenyl)picolinateC15H13ClF2NO2ClC1=CC(=NC(=C1Cl)C1=CC=C(C=C1)OC)C(=O)OC(C)Cisopropyl 4,5-dichloro-6-(p-methoxyphenyl)picolinateC16H16F2NO3ClC1=NC2=CC=CC=C2C=C12-chloroquinolineClC1=CC=NC2=CC(=CC=C12)C(F)(F)F4-chloro-7-(trifluoromethyl)quinolineClC1=NC=CC2=CC=CC=C121-chloroisoquinoline3-chloro-6-phenylpyridzaineClC1=NC=CC=C1C(F)(F)F2-chloro-3-(trifluoromethyl)pyridineClC1=NC=C(C=C1)C(F)(F)F2-chloro-5-(trifluoromethyl)pyridineClC1=NC=CC(=C1)C#N2-chloro-4-cyanopyridineClC1=NC=CC=C1C#N2-chloro-3-cyanopyridineClC1=NC=C(C=C1)C#N2-chloro-5-cyanopyridineClC1=NC=CN=C12-chloropyrazine[N+](=O)([O-])C1=NC=CC=C1Cl2-nitro-3-chloropyridineClC1=NC=C(C=C1)I2-chloro-5-iodopyridineClC1=NC=C(C=C1)[N+](=O)[O-]2-chloro-5-nitropyridineClC1=NC=C(C=C1)Br2-chloro-5-bromopyridineClC1=NC(=CC=C1)Cl2,6-dichloropyridineClC1=C(C#N)C=CC=C12-chlorobenzonitrileClC=1C=C(C#N)C=CC13-chlorobenzonitrileClC1=CC=C(C#N)C=C14-chlorobenzonitrile[N+](=O)([O-])C1=CC=C(C(=O)OCC)C=C1ethyl 4-nitrobenzoate[N+](=O)([O-])C1=CC=C(C(=O)C2=CC=CC=C2)C=C14-nitrobenzophenoneOTf[F]fluorinearylproductnitroarenearyl fluorideproductC6F6aryl chloridesaryl triflatearyl bromidesaryl ether2-substituted pyridines[N+](=O)([O-])C1=NC=CC=C12-nitropyridinearyl bromidehalide[N+](=O)([O-])*nitroC(C1=CC=CC=C1)OC=1C=CC=C2C=CC(=NC12)Cl8-(benzyloxy)-2-chloroquinolinearyl chloridenitroarene substrateC(C)(=O)OCCethyl acetate1H[13CH4]13CEtOAcaryl halidesnitroarenesO=[N+]=ONO2ClClBrBrClCCldichloromethaneTeflonCDCl3C[S](C)=ODMSOFC1=CC(=CC(=C1)F)F1,3,5-trifluorobenzeneC1(=CC=CC=C1)CtolueneCN(C)C=ODMFEt2O1H, 13C[ M + H]+ calcdCCCCCChexanesCC(=O)N[C@@H]1[C@@H](O)[C@@H](F)C(O[C@H]1[C@H](O)[C@H](O)CO)(O[P](O)(=O)OC[C@H]2O[C@H]([C@H](O)[C@@H]2O)N3C=CC(=NC3=O)N)C(O)=OCsF19FNMe4FnitroarenesusinganhydroustetramethylammoniumfluorideanhanhydrousTBACNtetrabutylammoniumcyanideCMNHCsN-heterocycliccarbenesCManhandMarshallhavereportedthatNMe4Fi.einitiallyexaminedat140°CCOMcostofmanufacturinganhand5dwithCsFandNMe4FanhandnitroarenesreactwithNMe4FanhanalysisprojectsthatNMe4FppmpartspermillionAmerican Chemical Society10.1021/acs.joc.5b020752015-12-09T00:00:0091a34bdb-ba93-4833-b344-91857404f3f2.htmlSydonie D. SchimlerSarah J. RyanDouglas C. BlandJohn E. AndersonMelanie S. Sanford