碳負(fù)離子縮合反應(yīng)

1、CHRCOHCHRCOHBCHRCOCHRCOpKapKaHCH2CH3HCH2CHCH2HCH2HCH2CNHCH2SCH3OO 3550293425HCH2COC2H5OHCH2CCH3OHCH2COHCH2NOO201610.224CH2NOHBCH2NOCH2NOCH2CHBCH2CNNCH2CNCH2SH3COHBCH2SH3COCH2SH3COOOOOOOpKaH2CCCH3OH2CCOC2H5OC2H5OCCHOCOC2H5OH3CCCHOCOC2H5OH3CCCHOCCH3OHHHHH242012.710.79.0CHCH3COHCCH3OBCHCH3COCCH3OCHCH3C

2、OCCH3OHCCH3COCCH3OCH2CH3COHBCH2CH3COCH2CH3CO 強(qiáng)堿可使羰基化合強(qiáng)堿可使羰基化合物完全烯醇負(fù)離子化物完全烯醇負(fù)離子化Na NH2Li NCH(CH3)2CH(CH3)2(LDA)SOCH3Na CH2Na HNaOHNaOR用于活潑用于活潑a a-氫的烯氫的烯醇負(fù)離子化醇負(fù)離子化（如（如b b-雙羰基化合物）雙羰基化合物）OCH3B:OCH3OCH3+CH2CH3CORB:CHCH3CORCHCH2COR+CHRCOCHRCOCHRCO ECHRCOCHRCOE或或ECCOR(H)D2O /DOCCOR(H)HDH2O /HOOCH3OD / D2O（

3、過過量量）OCH3DDDCCOODDOCCOHCCODD- - HOD+DOCCORR1HR2/ HBB:CCORR1HR2orOH,RO*旋光性消旋化 CCORR1BCCORR2R1HR2CCORR2R1HH*BHB: CCOCCOHCCOXXOHXCCORHRCCORHHCCOHHH CCOHX2 ，OHX = Cl, Br, ICCOXOHCH3COR3 X2CHX3CORO+CH2CORHOCX3CORCOROHCX3COROHCOROCHX3+HOCH2CORXXCHCORXCX3HHOH+CCORCCORRXCCORR強(qiáng)強(qiáng)堿堿H XCCOROHCCORORXCCOROR強(qiáng)強(qiáng)堿堿 X

4、第一步若不采用強(qiáng)堿和低溫，酮將不能完全烯第一步若不采用強(qiáng)堿和低溫，酮將不能完全烯醇負(fù)離子化，會(huì)發(fā)生醇醛縮合等副反應(yīng)。醇負(fù)離子化，會(huì)發(fā)生醇醛縮合等副反應(yīng)。OCH3O強(qiáng)強(qiáng)堿堿 / / 低低溫溫ONaCH3I如如：NaNH2, LDA, NaH, Ph3CNa等等CO2EtLDA / -78oCCO LiEtOCH3IEtO2CCH3OCH3堿OCH3OCH3+R XR XOCH3ROCH3RCOCCOCOCOCHBRXCOCCORCOCCHNCNCCHNArCCHNH3CCH3OOCH3IH3CCH3OOCH3H3COC2H5OOCH3(CH2)3BrNaOEtH3COC2H5OO(CH2)3CH

5、3NCOC2H5ONaOEtClCH2ClNCOC2H5OClK2CO3CH2CO2C2H5OCD3ICO2C2H5OD3Ct-BuOKCCOH+COCCOCOHOHCCOCorH2CCHOH+H3CCHOCH2CHOCHOHH3COHCCOHHCCOHCOHCOHCCOCCH2or2HH- H2OCH3CH2CH2CHO2KOHCH3CH2CH2CHCHCHOHOC2H5C7H15CHO2NaOEtC7H15CHCCHC6H13OCH3CH3OOKOHCH3OCH3OHCH3OCH3- - H2OCH3CCH3O2Ba(OH)2CH3CCH3OHCH2CCH3OI2CH3CH3CCHCCH3

6、O 不能直接脫水不能直接脫水丙丙酮酮Ba(OH)2CCOCCOHHHCCOHCBCOOHBCCOHCHOBCCOC OHCCOCHOCCOHCCOCOHCCOHHOHCOCCOHCOHOHHOHOHHCCOCR2OR1OHR4OR3+R2OR1R3OHR4R4OR3R1OHR2R2OR1R3R4R4OR3R1R2PhC HO+CH3CH3CH2CONaOHCCCH3CH2COHPhHPhC HO+CH3CPhONaOHCCCPhOHPhHH2CO3+CH3CHONaOHCCHOCH2OHCH2OHCH2OHNaOHCHOCHOPrPrCHOH2OOCH3OO或CHOPrOHH+ 或 OH- -不能消除不能消除H2OOCH3HOOHH3COOH3CHOOLDA / 70o C醚O Li(1) CH3CHO(2) H2O, HOOHOCH3(1) LDA / 70o C(2) ClSi(CH3)3OSi(CH3)3CH3(1)PhCHOTiCl4OCH3PhOH(2) H2O, HOOHOOHOOCH3OCH3OCH3OOHOOHOOOOHOOHOOCH3OOOOHOOOHOHOOOOOOOOOOHHOOHOHOHOO OHOOHOCH3OCH3CH3OCH3OCH3CH