手性合成英文

EliasJ.Corey

－－Autobiography

1928 borninMethuen，Massachusetts1944 enteredM.I.T. 參與合成青霉素1950 completeddoctoralworkjoinedUniversityofIllinois1956 becameProfessorofChemistry1959workinHarvard

11957年EliasJ.Corey提出了他的想法：TheLogicofChemicalSynthesis

retrosyntheticanalysis

逆合成法2Thelogicofchemicalsynthesis簡(jiǎn)單的原料

復(fù)雜的分子

transformsynthesis反合成分析法retrosyntheticanalysis

3retrosyntheticanalysis4Retrosynthetictree

樹(shù)根－－目標(biāo)分子樹(shù)枝－－原料BestChoice?5位置控制

保護(hù)基活化基橋連因子67Tobuild"left-orrighthanded"molecules

8910HerbertC.Brown

USAPurdueUniversity

WestLafayette,IN,USA1912-11GeorgWittig

FederalRepublicofGermanyUniversityofHeidelberg

Heidelberg,Germany1897-198712TheNobelPrizeinChemistry1979Laureates:HerbertC.Brown

GeorgWittig

"fortheirdevelopmentoftheuseofboron-andphosphorus-containingcompounds,respectively,intoimportantreagentsinorganicsynthesis"13

BoroncompoundsHerbertCBrownsodiumboro-hydride(硼氫化鈉)--thereagentofchoiceforreductionofcarbonylcompoundsOrganoboranes(B2H6)(themostversatilereagentsevercreatedinorganicchemistry)14canbeusedforreductions,rearrangementsandadditionsandhaveopeneduparangeofnewpossibilitiesforlinkingcarbonatomstoeachother.還原重排加成15Wittigreactionorganicphosphoruscompoundwithaformaldoublebond(含雙鍵的有機(jī)磷化合物，雙鍵在P和C之間)betweenphosphorusandcarbonreactwithacarbonylcompound(羰基化合物).Theoxygenofthecarbonylcompoundisexchangedforcarbon,theproductbeinganolefin(烯烴)。16

這是我們熟悉的Wittig試劑，用于雙鍵化合物的制備Acarbonyl

compound(羰基化合物)organicphosphoruscompoundwithaformaldoublebondbetweenphosphorusandcarbonolefin(烯烴)17Fig.1.Formationofadiradical被削弱的C-C鍵18demetalization

有機(jī)金屬鋰化合物

diradical19Formationandcharacterizationofcompound9zincdustdistillation.20芳基質(zhì)子作為取代基的不穩(wěn)定性驚人發(fā)現(xiàn)：umpolung規(guī)則或極性逆轉(zhuǎn)規(guī)則F的特異性21Reversalofpolarity(umpolung)極性逆轉(zhuǎn)22Mechanismofformationofo-lithiobiphenyl23Proofoftheintermediateoccurrenceofdehydrobenzeneinthereactionof14C-labeledchlorobenzenewithpotassiumamideinliquidammonia24Fig.8.Proofoftheexistenceofdehydrobenzenethroughtheformationof10苯炔中間體存在的證實(shí)：在反應(yīng)過(guò)程中加入二烯體呋喃，分離出產(chǎn)物10aDiels-Alderaddition：25經(jīng)證實(shí)，苯炔中間體存在的時(shí)間為：20milliseconds.

Thermaldecompositionreactionsusedtodeterminethelifetimeofdehydrobenzeneinthegasphase26四烷基銨鹽上的碳上的氫是否也有不穩(wěn)定性？通過(guò)：氯化四甲基銨甲基鋰

五甲基氮

失?。?7FormationofNylides28ylide29FormationofP-ylides30N-ylide(氮葉立德)ThesemipolarnatureoftheN-CbondItsabilitytoaddtobenzophenone（二苯甲酮）31P-ylide（磷葉立德）triphenylphosphinemethylenetriphenylphosphineoxide1，1-diphenylethylene32

Fig.13.Stepsinthereactionoftriphenylphosphinemethylenewithbenzophenone四元環(huán)過(guò)度態(tài)33應(yīng)用：vitaminA的合成

34硼也可以作為

tetracoordinatecentralatom35參考文獻(xiàn)E.J.Corey,X.-M.Cheng:TheLogicofChemicalSynthesis,Wiley–Interscience,1989.E.J.Corey,A.K.Long,S.D.Rubenstein:Computer-AssistedAnalysisinOrganicSynthesis,Science,Vol228,1985,pp408-418.TheRoyalSwedishAcademyofSciences,InformationabouttheNobelPrizeinChemistry1990(pressrelease).

36FurtherreadingG.WittigandM.Rieber,ibid.562,187(1949).G.WittigandKClauss,ibid.577,26(1952);ibid.578,136(1952).G.WittigandK.Torssell,ActaChem.Stand.7,1293(1953).H.Pommer,Angew.Chem.89,437(1977).R.W.Hoffmann,Dehy