PERICYCLIC-REACTION2【课件】有机合成(上海有机所)

1,3-dipolaradditions1,3-dipole:4p-electronsaredistributedover3atomsCH2=N=NCH2NNCH2NNOOOOOORCNORCNNR'RNNNRNO-OLUMOHOMO1,3-dipoledieneThereactionsof1,3-dipolesCH2N2CH2=CH2NNNNH+CH2NNCH2N2CH2=CHCO2CH3NNCH3O2CNNCH3O2CH+CH2=CH2+O3OOORCNO+RN3CCNNNCCR+CCNOCCRRCNOIII.ElectrocyclicreactionCH3CH3CH3CH3CH3CH3heathCH3CH3CH3CH3heathCH3CH3cistranstranscisy1y2y3y4HOMOLUMOBondingorbitalsAnti-bondingorbitalsHOMOconrotatoryy2heatHOMOdisrotatoryy3hCH3CH3CH3CH3heatcon.CH3CH3CH3CH3hdis.y1y2y3y6y5y4HOMOLUMOy3disrotatoryheatHOMOy4HOMOconrotatoryhCH3CH3CH3CH3heatdis.CH3CH3hCH3CH3con.Numberofpelectron4n4n+2HeatIrradiationconrotatoryconrotatorydisrotatorydisrotatory4heatconrotatoryClClhdis.CO2EtBrCO2EtBrheatdis.EtEtheatEtEtcon.HHheathCH3CH3CH3CH3IV.Sigmatropicrearrangements?C2H5heatC2H5C2H5heatC2H5+Sigmatropicarrangement1,5-HshiftCH3Hheatheatcon.Dienep-LUMOC-Hs-HOMO1.[1,j]-sigmatropicrearrangementsC9H17CH2HOC9H17CH3HO[1,7]shiftVitaminDPrecalciferol2.[i,j]sigmatropicrearrangementsRRheat[3,3]sigmatropicrearrangementsTheCoperearrangementheatCH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3CH3cis,transtrans,transcis,cisOEtOOOH+OOOOOOHOOOHCO2OOHOMeOOOOHreductionOMeOOetcTheClaisenrearrangementOOHtautomerismOHOOHtautomerismOHOOHheatOCH3CH3CH3CH3OHheatOCH3CH3OCH3CH3HV.EnereactionandrelatedreactionsH+HHHOR+HRHOheatROHOHORheatROOH+OHOROheatRCH2OHCO2RCOCH3TheCopereaction(CH3)2NO-CH2CHHCH2CHCH2heat(CH3)2NOH+