手性磷酸催化剂在不对称合成中的应用

:200711,:2007123e2mail:[e-mail]3(200240)2004Br«nsted,,MannichPictet2SpenglerStreckeraza2Diels2AlderFriedel2Craft2:O62113+4;O643136;O613162:A:10052281X(2008)1021534210ApplicationofChiralPhosphoricAcidinAsymmetricSynthesisChenXiaofenLiuZengluMaoZhenmin3(SchoolofPharmacy,ShanghaiJiaoTongUniversity,Shanghai200240,China)AbstractThechiralphosphoricacidisafairlystrongBr«nstedacidwithnovelstructurewhichwasfirstreportedin2004.Ithasbeendevelopedrapidlyinrecentyearsandbecomeaveryimportantbranchoforganocatalysis.Excellentenantioselectivitiesandgoodyieldscanbeobtainedinaseriesofasymmetricadditionandreductionreactionsofimineswhencatalyzedbychiralphosphoricacidcatalysts,suchasMannichreaction,asymmetrictransferhydrogenationreaction,hydrophosphonylationreaction,Pictet2Spenglerreaction,Streckerreaction,aza2Diels2Alderreaction,Friedel2Craftreaction,alkylationofdiazoesterreactionandsoon.Inthispaper,thelatestprogressintheresearchofchiralphosphoricacidcatalystsforrelevantasymmetricreactionsisreviewed.Keywordschiralphosphoricacid;imines;asymmetriccatalysis,,,,,,,,,[1],3,Br«nsted,[2],,,,2010200810PROGRESSINCHEMISTRYVol.20No.10Oct.,2008©1994-2008ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[3],1a,,10mol%,296%ee(1)Br«nstedMannich2type,Br«nsted1Mannich2type[3]Fig.1AsymmetricMannich2typereactioncatalyzedbychiralphosphoricacid[3]2Mannich2type[4]Fig.2MechanisticassumptionoftheMannich2typereactioncatalyzedbychiralphosphoricacid[4]3,32,;,NOH,[4](2):,1aMannich2type,2005(+)TADDOL2[5]TADDOL(BINOL),422Mannich2type(3),OH,,3Mannich2type[5]Fig.3AsymmetricMannich2typereactioncatalyzedbychiralphosphoricacid[5]4Mannich[6]Fig.4Asymmetricdirect2Mannichreactioncatalyzedbychiralphosphoricacid[6]Mannich2type,MannichAkiyama,Terada[6]1bN2Boc(N2):2mol%,99%,95%ee,,(4):(1)P()4,P;(2)H,;(3)POOLewis,,,535110©1994-2008ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[7]Mannich(56)5Mannich()[7]Fig.5Asymmetricdirect2Mannichreactioncatalyzedbychiralphosphoricacid(cyclicketone)[7]6Mannich()[7]Fig.6Direct2Mannichreactioncatalyzedbyphosphoricacid[7],015mol%1c2mol%3a,Mannich,2,98%ee22.1CN,MacMillan[8],H,(NADH)HEH(Hantzsch)H,,60%87%,83%97%ee;,(7)7[8]Fig.7Asymmetricreductiveaminationreactionofketonecatalyzedbychiralphosphoricacid[8]2006List[9],Hantzsh4aH,1e,,,98%ee,96%(8)8[9]Fig.8Asymmetricreductiveaminationreactionofaldehydecatalyzedbychiralphosphoricacid[9]2.2,Rueping[10]List[11],,List:1e,35,,,,,635120©1994-2008ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(9)(PMP)9[11]Fig.9Asymmetrictransferhydrogenationreactionofiminescatalyzedbychiralphosphoricacid[11],Rueping[12],,2mol%,22(10)10[12]Fig.10Asymmetrictransferhydrogenationreactionofquinolinecatalyzedbychiralphosphoricacid[12]:,HantzschHantzsch,Hantzsch;,Hantzsch(11)2006,Rueping[13],1f,,93%99%ee,,10mol%0101mol%,(12)2007,Rueping[14],,92%ee(13)11[12]Fig.11Mechanisticassumptionoftheasymmetrictransferhydrogenationreactionofquinolinecatalyzedbyphosphoricacid[12]12[13]Fig.12Asymmetrictransferhydrogenationreactionofheterocycliciminescatalyzedbychiralphosphoricacid[13],,13[14]Fig.13Asymmetrictransferhydrogenationreactionofpyridinescatalyzedbychiralphosphoricacid[14],2735110©1994-2008ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[15]2(14)142[15]Fig.14Asymmetrictransferhydrogenationreactionof2iminoesterscatalyzedbychiralphosphoricacid[15]2,1h85%98%94%99%ee322,,,Akiyama[16],2(15),,,;NOH,MannichNOH15[16]Fig.15Asymmetrichydrophosphonylationreactionofiminescatalyzedbychiralphosphoricacid[16]4PictetSpenglerPictet2SpenglerLewisBr«nsted,2006,List[17]22,1e22(16),,,,86%90%ee;,,2216Pictet2Spengler[17]Fig.16AsymmetricPictet2Spenglerreactioncatalyzedbychiralphosphoricacid[17]5Strecker2,,,Strecker2006,Rueping[18]Strecker,,,1f(17),,,17Strecker[18]Fig.17AsymmetricStreckerreactioncatalyzedbychiralphosphoricacid[18]835120©1994-2008ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[19],,(18)18[19]Fig.18Asymmetricamidationreactioncatalyzedbychiralphosphoricacid[19]7BiginelliBiginelli,3,42222(1H)2(DHPMs)2007[20]Biginelli,,H82Binol3aBiginelliBinol:,;;2,,97%ee(19)19Biginelli[20]Fig.19AsymmetricBiginellireactioncatalyzedbychiralphosphoricacid[20]Biginelli(20):,,2,,Br«nsted20Biginelli[20]Fig.20MechanisticassumptionoftheasymmetricBiginellireactioncatalyzedbychiralphosphoricacid[20]8Friedel2Craft(F2C)Friedel2Craft,F2C:N2Friedel2CraftFriedel2Craft,Friedel2Craft2007Terada[21]Friedel2Craft:,F2C,(21)21Friedel2Craft[21]Fig.21Friedel2Craftreactioncatalyzedbychiralphosphoricacid[21]:,;(DMFDMSO),:935110©1994-2008ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[22]F2C,2006Deng[23]32,,10min,99%ee,;,50%(22)22Friedel2Craft[22]Fig.22Friedel2Craftreactioncatalyzedbychiralphosphoricacid[22]2007,Antilla[24]N2N2,N2,,;;N,(23)23Friedel2Craft[24]Fig.2