金属有机化合物在有机合成中的应用

3,,()():,,,J,.,IAIAIAIA,MC,,1.,CCRX+RZM,RlR+MXCC¹,:l,,,.,,JEt20~,º,,G:1,5,,::3x,.Li+,\cl(88,t111//OH(70%0H_LTIEDA_BZU~50%),,a,[1SPI-*+:SPhZ(82%ENHZ/,(70%)»,,,Li,Na,KMg:[JSee~BuLiArBr+RBr,ArR\nc8H7x-~qHz7(XB:,x)(100%)2.:,{lRM+RCY/O,RCRtOHOH!C,R~RIY,RlCRl1R1¹*TMEDA3OMHZOllRM+RZCOYRCY,R,CRZ(Y=OH,OR,SR,NR:,CN)1R2,,(OHRMRlCRZRl}CR{lR:CoXCooRCoNH:eN),B,AI,Si,Sn,Zn,Cd,Hg,Cu,Zr,Fe,Rh,Pd:56R:ZnRCOCI~RCOR{}RCOCN+RMgX-~RCR(7084%)R/MgX3HMPARCOY~RCOR(6395;):7](YCI,OAe,OMe.NMe:)ºIAIA,,,[:COLi{!(88%)}{1OHCram,R,,!l:MeLiz/OH\\M.M(,4%)0H(6%),HMPA1,s....,...,,.,,J.,,.,,.,..,.,,......,,........»,,F,,,EtLiBuLi,,[JRLi+CH:CH:~RCHzCHzLi(R=iPr,CCoH;:,tBu)1:-[1RZRLi,TMEDA}C!I:=ClCZOHLlCH:CHCH:01iR}CH3CHCHZOHHZO/\CO:\/,:.CHCH/CH3CHCHzCCHZ,(3.aIAIACH,HCC,a,a,}1MC~:C+MX}X3RX\RCN!__CCR}11ZNM!C|ZR{RCOXRCOC!ZR1}!RCOR:RlCC~-{}M02}MC1Z\/ROOMCCCOO}{}CCCCOM}Z,,.})C-ZOMC=CMOZC12CMJ--\__,J/O}}/C/\OM~C!|Z|C021|,e/CMCCCCCCZC/}//¹a,NaCNKCNRX-RICORZRCNMCN,\//~\\R}C=O--OMCN{1!NCCCCO!1lC!Ca,1,41,aMX+/O}}}RCH:NO:,RCH=N(M+CCC=0_____~~R}!!102NCCCC=O!H2/S\/R\_s/\HnBUL--THF,30~OOC/S\/R\_s/\Li2/S\s\//\\//\\\//RRX\1\R1CNlC!C!C/S\/R\_s/\coR,/S\/R\s/\cRR,1OHRCOX///S\/R\_s/\Li~RUSSR\/COR,0H!n:,/J2.J//_/\s/\/\R,S\/Rs/\ccc/{!}OHS,S,1,4,1,2[161ºaC,,a@,CSnBuLiRCHZCOCHZSOnR---,RCH:COCHSOnRLDA.Li1R:X~RCH:COCH:R.2AI(Hg)(n1,2)a1LDA*R,CH:COCZSOIR-~1RXRICHCOCHSO:R,RIRZCHCOCH:50:R2.nBuLi}}LiLAI(Hg)DLp:nKKH[72HZO*LJ)A31LDAPhCHZCOCH:SOZPh~2nBuLi3Br(CHZ):Br(b)[81Ph/s:OaCC./xLi+E+/\f.xE\xaSR,SoR,SoZR,SoR,PoxZa,oR,NRZ:50ZphCH3COCH3h(71%)L*,oHa,r,a.H.S~/HM-C,»a@a,,EI}:CHCHO+NaCHCOOMI~DMEP(O)(OEt):H)CC(96)%E)COOMea,,.%R1CORZ+MCH(SIMe3):,RIRZC=CHSIMes.LDAh1,54(b)2,32,3LiCHCHZCRRICHCHz[31,CRlHOAC!/\R[X!/\SOZPh00-50:Ph00\_/\_/(C),;12R1\/-H,/\HCORR\oR502~/soa.\2RNOLLi_A¼aRCORZ+KCRCOOEt,RRCCR3COOEtRRZCHCOR!\/XO[25,:RCOR:1.MCHZSOR2RX,RRCCH\/O½CCCMH,MXRtcpeHRZiCM,,R,eeHR:!!BrOLiLiN(Pri)2(LDA),LIN(SIMea):,KN(SIMe3)2OLi(85%)(8%LDAŽ”O(a)C0,:,,,3OCH:PhDMF/~+PhCHZLr/97%,CHZPhOCH:Ph\CFsCHZOHOHO(85%),aa12!(7%)OK1MeC=CHPhCIhvMeeH:P(68%)(b):R|R|OR4CORS,RCCCOMRCOX~~~~--~-~~!RRORO!}1{{RICCCR/\RaM!”O|CRl}RKOH-----~~~~-~~,,-O~,,,,1.¹:Li,Na,K,Mg,Ca,Zn,AI,Sn,Ti,Fe,,!11)11rJ/....----~..--~~~1084º,,[,,:0Li,NH3r:?otBuOH!,8»,,tBuoHHMPA.,25OCa,:Li,NH3~~.-~-~,...Bu0HH,19:MeO/,///Meo,NHCI,:¾@@[2:,Hc.Nl2”Lt.1.....OHLi,NH3¼CO,n.,,NaNH,,,,,rnZ2----rn3nCO:.}3R:CHOH1.CIPO(NMe:):2.Li,EtNHZ,R:CH:CS:Li)EtNH32.¹,nBuCLiI2THF~nBuCCln,,,,.BrZ,,,rnz=ILI-~rnZIDr(94%)º,CMMe::me,PhssphMeselCS,[3,]:COOMeC00lSMen,!]:/\/\/\/\/\KNH)a2,/\/\/\/\/\/K,CH3(CHZ)CC(CH:)CCHNaNHZCH:(CHZ)ZCC(CHZ)CCNaH(CH:)CCH/\\/lNa,NH2H3O+CH(CHZ)2HCC(64)G4J_4PaceNaa185Cyoth.C\V.,84,4,11.CMP,84,4,3-,,CMR,48,,9.3,,,,C&EN,SJ,J,?3..;.F:.1,CMR,84,,16,CR,,8,J,30.19841983.90%.4%,84,5,8.,15.861.09:::::C.W.CI:emiealWeok()C&EN:CllemiealandEngineerinzNews()ECN:EuropianChemiealNew:()CMR:ChemiealMarketingReporter()(59),.osawa,E.,etal.,J.O:9.Chem.,36,205(1971)2.Akiyama,5.,etal.,Tetralied:onLeett.,4115(1973)3VanTamelen,EE.,etal.,J.AmChemSoe.,96,2215(1974).4Biellman,J.F,etal.,TetrahedronLett.,3707(1969)AltmanL.,etal.,Snthesis,]?9(174).5.Merrill,R.E.,etal.,J.Org.Chem.,33,352(197)6Borth,R.F.,etal.,J.org.Chem.,37,725(1972)7.Huetg,F.,et.,Tetrahedron,23,79(1573).8.Bartlett,P.D,etal.,J.Am.Chem.Soe77,804(1958)9J.Maedounld,T.L.,etalJ.AmChem-Soe,97,5280(1975)10.Cram,D.J.,etal.,J.AmCmSoe,85274(1963)11.Drozd,VN.,etal.,Zhur.obsheh.Knim.28,2114(1968).2.Crandall,J.K.,etal.,J.org.Chem.,373334(1972).13.Lehmkuhl,H.,etal.,A:in,103,1191176(1975).14.Seebaeh,D.,Anw.Chem.Int.EdEngl.,9,639(1969)is.Gr6bel,B.T.,etal.,Svnthesis557(1077).16.Seebael,,D.,etal.,Angew.Chem.Int.EdEngl.,14,57(195).i7.Cooke,F.,etal.,Chom.Commun.,529(196)]8.Evans,D.A.,etal.,Aee.Chem.Res.,I-147(1974)19.Kato,T,etal,Chem.Letl.,1009(1977)?0.Gr6bel,B.T.,etal.,Synt!lesis(1977)21.Kinstle,T.H.,Chem.Commun.1699(1975).22.Tannka,K.,etal.,Chem.Lett.,i,7(2075)23.Kondo,K.,etal.,TetrahedronLett,1007(1975).24.Paquette,L.A.,Org.Reaet.,25,i(197)25.Johnson,C.R.,etal.,JAm.Chem.Soe.,95,4287(1973).26.Bunnett,J.F,etal,Chem.PharmBull,23,2621(1975)27Smid,J,J.AChenSoe,87,655(1965)-28Haffuan,J.G.,et,J.AmChenSoc90,6486(1968).2,.Harvey,R.G.,Svnthesis,262(1970).3o.Trost,B.M.,PureAPpl.Chem,s,563(2975)-sl.Nf,F.,et.,Helv.ChinlAeta,55,2005(975).