有機(jī)過(guò)渡金屬試劑的合成反應(yīng)PPT課件

1、1、羰基金屬絡(luò)合物Fe(CO)5 Ni(CO)4Fe: 3d6,4s2Ni: 3d8,4s2Na2Fe(CO)48+2+ 4 x 2 = 18 電子FeOCCOCOCOCONiCOCOCOOC六邊雙棱錐8 + 2x 5 = 18 電子10+ 2 x 4 = 18 電子鈉提供2個(gè)電子第1頁(yè)/共58頁(yè)2、-金屬絡(luò)合物 二烯丙基氯化鈀Pd: 4d8, 5s23+10+1=143+10+3=16d x2-y2 dxy， dyz， dxzZYXZYX二烯丙基鹵化鎳 Ni: 3d8, 4s216電子第2頁(yè)/共58頁(yè)FeTiClCl3. 二茂金屬化合物二茂鐵： Fe： 3d64s2Cp2Fe 8 + 5 x

2、 2 =18Cp2TiCl24 + 5 x 2 + 2 =16二氯二茂鈦一氫一氯二茂鋯Ti 3d24s2Zr 4d25s24 + 5 x 2 + 2 =16Cp2ZrHClZrHCl第3頁(yè)/共58頁(yè)二、基元反應(yīng)（1）配位和解離MLLLLMLLSL+L18電子體系16電子體系18電子體系解離（反應(yīng)時(shí)）配位（反應(yīng)物）產(chǎn)物反應(yīng)CoH(N2)(PPh3)3解離CoH（PPh3）3CCCCCoH(PPh3)3Co: 3d74S29+1+2+3x2=18 電子16電子使烯烴活化例第4頁(yè)/共58頁(yè)（2）氧化加成與還原消除Ir: 5d76s2IrLCOClL+RXIrLCOClLRX16 電子16 + 2 =

3、 18 電子M Ln+A-B氧化加成還原消除Ln MAB第5頁(yè)/共58頁(yè)（3）插入與反插入Ln MRABABLn MABRLn MARBPd：4d8 5s2PdLEtLEt16電子-L+COPdLEtCOEt插入PdLEtEtLCO16電子16電子第6頁(yè)/共58頁(yè)（4）絡(luò)合物中配位體的反應(yīng)Cr： 3d44s2CrClOCCOCO+NaOCH3CrOCH3OCCOCOMNu第7頁(yè)/共58頁(yè)二、一氫一氯二茂鋯Na+ZrCl4THFCp2ZrCl2LiAlH4Cp2Zr(H)ClSchwartz 試劑+Cp2Zr(H)ClCp2ZrCl1、鋯氫化反應(yīng)+ZrHZrHHZr16 電子18 電子16 電子

4、第8頁(yè)/共58頁(yè)RR1開(kāi)始開(kāi)始1:2過(guò)量過(guò)量 Cp2Zr(H)Cl 處理處理MeEt55:4589:11Men-Pr69:3191:9Mei-Pr84:1698:2Met-Bu98:2Cp2Zr(H)ClR1ZrHRR1HRHZrZrHR1RZr(RR)12+Cp2Zr(H)ClRCCR1Cp2ZrRR1HClCp2ZrR1RHCl+第9頁(yè)/共58頁(yè)2、還原反應(yīng)可以還原醛、酮、酸、酯、腈等化合物由于上述還原反應(yīng)速度與鋯氫化速度近似，若分子中有C=C存在必須保護(hù)OR1R+Cp2Zr(H)ClCORR1HCp2ZrClH2OCHOHRR1RCH2CN+Cp2Zr(H)ClCHCH2RNCp2ZrC

5、lH2ORCH2CHO第10頁(yè)/共58頁(yè)三、烴基氯化二茂鋯Zr-C鍵斷裂可產(chǎn)生一系列反應(yīng)1、鹵代反應(yīng)Cp2ZrHRCp2ZrHRI2Br2NCSRIRBrRCl91%92%67%（R = C6H13 ） 若R為手性碳，鹵代時(shí)可保持構(gòu)型第11頁(yè)/共58頁(yè)ZrCpClCpCBr2ZrCCpCpBrBrClCBr保持構(gòu)型18電子Cp2ZrH3CPr-iHClNBSBrH3CPr-iH95%第12頁(yè)/共58頁(yè)2、氧化反應(yīng)RCp2ZrClH2O2/NaOH或t-BuOOHOCp2ZrClRH2OROH第13頁(yè)/共58頁(yè)3、插入反應(yīng)RCp2ZrClCOCp2ZrClRH3OCOBr2CH3OHH2O2RR

6、COOCH3RCOOHCOHRCORCp2ZrClAg+OOCH2CH2RCp2ZrClH3ORCH2CH2OH第14頁(yè)/共58頁(yè)4、金屬轉(zhuǎn)移反應(yīng)中的R基團(tuán)可轉(zhuǎn)移到更活潑的金屬上。RCp2ZrClR*Cp2ZrCl+AlCl3CH2Cl20 0CR*AlCl2+ Cp2ZrCl2COR*Cp2ZrCl+AlCl3CH2Cl20 0CR*COAlCl2+ Cp2ZrClR*AlCl2RCOClR*COAlCl2H3OR*COHR*COR第15頁(yè)/共58頁(yè)5、偶聯(lián)反應(yīng)HR1HZr+ArXNi(PPh3)4HArR1HHR1HZr+XHR2R3Pd(PPh3)4HR2R3R1HH第16頁(yè)/共58頁(yè)四

7、、二氯二茂鈦制法1、亞甲基轉(zhuǎn)移反應(yīng)Na+TiCl4Cp2TiCl2Tebbe 試劑（亞甲基轉(zhuǎn)移試劑）Cp2TiCl2+ 2 AlMe3Cp2TiH2CClAlMeMe+CH4+ Me2AlCl第17頁(yè)/共58頁(yè)Cp2TiClAlMeMeRCORRCONR2RCOOR1OCH2OOCH2RRCCH2RNR2CCH2ROR1第18頁(yè)/共58頁(yè)OH3COOCp2TiCl2AlMe3H3COH3COCp2TiCl2AlMe3OCH3OOCH3OClaisen Rearrangement第19頁(yè)/共58頁(yè)Carbonyl methylenation: Petasis reagentDifficultie

8、s with the Tebbe and Grubbs Ti-mediated olefinations include the high cost of Ti reagent, long preparation times, short shelf life, and the need for special techniques due to sensitivity to air and water. Many of these difficulties are overcome with Petasis procedure which uses dimethyltitanocene. P

9、etasis JACS 1990 112 6392.第20頁(yè)/共58頁(yè)第21頁(yè)/共58頁(yè)P(yáng)etasis JACS 1990 112 6392.第22頁(yè)/共58頁(yè)第23頁(yè)/共58頁(yè)Hughes OM 1996 15 663.第24頁(yè)/共58頁(yè)2、-烯丙基鈦絡(luò)合物的反應(yīng)Ti: 3d24s218 e第25頁(yè)/共58頁(yè)3、Cp2TiCl2催化下LiAlH4、NaBH4的反應(yīng)+Cp2TiCl2LiAlH44 RCHCH2LiAl(CH2CH2R)4H2OCu(OAc)2Cu(OAc)2COCu(OAc)2CHOCH3ONaH2O2RRRORCHOROHRROHLiAl(CH2CH2R)4第26頁(yè)/共58

10、頁(yè)Cp2TiCl2+LiAlH4Cp2TiHClCp2TiCH2CH2RClRCHCH2LiAlH4RCH2CH2AlH3Li第27頁(yè)/共58頁(yè)4、Cp2TiCl2催化下RMgX的反應(yīng)i-PrMgBrO+Cp2TiCl2OH+OH95:5（1）、 C=O的還原+Cp2TiCl2MgBrCp2TiCl+CHH3CH3C+MgBrCl15 電子+MgBrCp2TiClCp2Ti+MgBrClCp2TiCp2TiH+CH3CHCH2第28頁(yè)/共58頁(yè)i-PrMgBrROCH3CO+(過(guò)量）1. Cp2TiCl22. H3ORCH2OH2 i-PrMgBrROHCO+1. Cp2TiCl22. H3O

11、RCHOCp2TiOCHRR1CH3CHCH2Cp2TiHORR1Cp2Tii-PrMgBrBrMgORR1HOHCRR1第29頁(yè)/共58頁(yè)（2）碳氮重鍵還原NR2R1R+i-PrMgBr1. Cp2TiCl22. H2OCHNHR2RR1RCN+i-PrMgBr1. Cp2TiCl22. H2ORCHOCC（3） 鍵還原CH3CCPh+ i-PrMgBr Cp2TiCl2HH3CPhMgBrEHH3CPhE第30頁(yè)/共58頁(yè)五、羰基金屬化合物1、一苯三羰基鉻（1） 環(huán)上的親核取代反應(yīng)第31頁(yè)/共58頁(yè)機(jī)理第32頁(yè)/共58頁(yè)（2）環(huán)上氫的酸性增加HCr(CO)3Yn-BuLiLiCr(CO)3

12、YEECr(CO)3YY: OCH3, ClE: CO2PhCHOCHPhOHCOOH產(chǎn)物：第33頁(yè)/共58頁(yè)（3 ）側(cè)鏈上-氫的酸性增加CH2COOCH3Cr(CO)3NaH/DMFBr(CH2)3BrCr(CO)3COOCH3Ce 4+COOCH387%（4）側(cè)鏈上共軛雙鍵的親核加成Cr(CO)3LiCNCr(CO)3CN1. E2. I2CNE第34頁(yè)/共58頁(yè)RX+Ni(CO)4RCONi(CO)3XRCOR1COXBr2ROHCOCORR1RCOORRCOCH2CH2YH2CCHY2. 羰基鎳、羰基鐵化合物（1） 與鹵代烴的反應(yīng)Ni: 3d84s2第35頁(yè)/共58頁(yè)Ni(CO)4Ph

13、COCH2BrPhCOCH2CH2COPhR3R4ArR5R4R3OR1R2R1R2R3R4OR1R2R1R2ArR5R3R4（2） 與-鹵代酮的反應(yīng)第36頁(yè)/共58頁(yè)（3） 與有機(jī)鋰化物的反應(yīng)RX+Ni(CO)4(CH3)2NLi(CH3)2NCNi(CO)3OLiRCON(CH3)2ArLi+Fe(CO)5ArFe(CO)4LiArCOFe(CO)3LiHRXArCORArCHOArCOCH2CH2YCH2CHY第37頁(yè)/共58頁(yè)C-H activation: Process where a strong C-H bond (90-105 kcal/mol) undergoes subst

14、itution to produce a weaker C-M bond (50-80 kcal/mol).Functionalization: Metal-C bond is replaced by any bond except C-H.C-H activation第38頁(yè)/共58頁(yè)Bergman:C-H Activation via Late, Nucleophilic ComplexesBergman Acc. Chem. Res. 1995 (28) 154.Bergman JACS 1982 (104) 352 . Bergman OM 1984 (3) 508 Graham JA

15、CS 1983 (105) 7190 (Cmp. 3).Bergman JACS 1994 (116) 9585 (Cmp. 4).第39頁(yè)/共58頁(yè)第40頁(yè)/共58頁(yè)Dehydrogenation of alkanes to alkenes第41頁(yè)/共58頁(yè)Tanaka: photochemical dehydrogenationGoldman JACS 1992 (114) 9492.第42頁(yè)/共58頁(yè)第43頁(yè)/共58頁(yè)Dehydrogenation of n-alkanes to terminal olefinsGoldman, A. JACS 1999, 121, 4086.第44頁(yè)/

16、共58頁(yè)第45頁(yè)/共58頁(yè)Direct carbonylation of benzeneEisenberg JACS 1986 (108) 535.第46頁(yè)/共58頁(yè)Tanaka Chem. Lett. 1987 249.Tanaka JACS 1990 (112) 7221.第47頁(yè)/共58頁(yè)第48頁(yè)/共58頁(yè)Direct carbonylation of alkanesTanaka JACS 1990 7221.第49頁(yè)/共58頁(yè)第50頁(yè)/共58頁(yè)Direct formation of aldiminesThe first report:Tanaka Chem. Lett. 1987 2373.第51頁(yè)/共58頁(yè)第52頁(yè)/共58頁(yè)Direct Borylation of Alkanes: CatalyticSmith JACS 1999 (121) 7696.第53頁(yè)/共58頁(yè)Hartwig Science 2000 (287) 1996.第54頁(yè)/共58頁(yè)Understanding and exploiting C-H bond activation