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1、TToottaallSSyynntthheesseessooffMMaannzzaamminineeAA..OPOABNRANW0OROMeRCin00NklerN,2HO,1NwaOHNhv998HHgaBka2]ENa+AHOH[4NDCM1NartiMeO2C99n,1,1CO2MeditE99an[4+9P]2]+2ABAB[4NNRCBnCONONmanzamineARCbzOROTBDPSRamilBaiazitov.SEDgroupmeeting.February21,2006MMaannzzaamminineeAA!-ca
2、rbolineNNHHBAHOHNDCNEmanzamineACHNO36444Haliclona(Sigmadocia)caeruleaExactMass:548.3515BlueCaribbeanspongeCaribbeanandHawaiianIslandsRings:Isolated:Higa,T.etalJACS,1986,108,6404eighttotal,fivealiphatic(ABCDE),one13-membered,one8-membered,β-carbolineTwoZ-doubleC-CbondsX-ra
3、yofStereocenters:HClsaltfiveoncarbon,fourcontiguous,onequaternary,onetetrasubstitutedMMaannzzaamminineeAAlklkaaloloididssNNNNNHHHHHNHHOHHONNN13NHN11811manzamineAmanzamineBmanzamineCNNHNHHNOHHHHHOHNHONNHNOmanzamineFmanzamineHMMaannzzaamminineeAAlklkaaloloididssHO2CNH2NH2NN
4、NNHHHHCHOCHOHHtryptophanHOHNDDQHOHHOHNNN1.Pictet-Spengler:37%N2.Ox:54%NmanzamineAircinolAircinalAantipodesNH2NNNHHHCHOCHOHHDDQHOHNHOHHOHNNHNHNHNircinolBircinalBmanzamineJKobayashi,J.etal.JOC1992,57,2480BiosyntheticHypothesisBiosyntheticHypothesisHO2CNtryptophanNNH2HNCHOHN
5、NH3CHOCHO11manzamineCdienophileCHOCHONNNH3CHO22OHCNH3NNCHOCHOddieipnoelarophileBaldwin,J.E.;Whitehead,R.C.Tet.Lett.,1992,33,2059BiosyntheticHypothesisBiosyntheticHypothesisdienophileHH!NNNNNH3ONSN2'dieneNNHO2CNH2keramaphidinBNN0.2-0.3%CHOH!NHHHHONNNNHHepoxideHNHNrearrange
6、mentOHNCHOHmanzamineBNOHNallylicoxidationSN2'HNmanzamineAircinalBBaldwin,J.E.etal.Chem.Eur.J.,1999,5,3154PPaannddiitt’’ssSSyynntthheessiissoofftthheeAABBCCDDEEffrraaggmmeenntt..RReettrroossyynntthheessiiss.."-carbolineno1,5-HshiftNNHHCO2MeCO2MeBHH[O][4+2]BnNAHOHOCO2MeNABZ
7、-dieneDCHNNOBnCNHONHchirality!NDDNECbzOHOHEOHmanzamineAHNNBnCO2MeBnCO2MeSOISOOONNHCbzSCbzOPOPOHO2CNH2Pandit,U.K.etal.Tetrahedron,OHL-serine1991,47,2005PPaannddiitt’’ssSSyynntthheessiissoofftthheeDDiieennee..COMeMeOOMe1.Ca(BH4)221.DIBAL-HPPTSCH2COOH2MeII2.NaBH4THF/EtOH,100
8、%1.HCl,100%NHCbzNHCbz2.I2,PPh3,Im,79%2.TBDPSCl,90%46%ONCbzNCbzNHCbzOTBDPS100%OTBDPSOOTBDPSxDIBAL
