有机合成化学学习教案

1、会计学1有机合成有机合成(yuj hchng)化学化学第一页，共90页。第1页/共90页第二页，共90页。MediatePromoteCatalyst第2页/共90页第三页，共90页。第3页/共90页第四页，共90页。第4页/共90页第五页，共90页。1 1、还原、还原(hun yun)(hun yun)反应反应NO2RNH2RMetalH+M = Zn Fe Sn 第5页/共90页第六页，共90页。RRRRNaNH3(l)第6页/共90页第七页，共90页。RRORROH+Zn-HgClaimenson Reduction第7页/共90页第八页，共90页。RRRRBrBrRRRRZn第8页/共

2、90页第九页，共90页。2 2、还原、还原(hun yun)(hun yun)偶联反应偶联反应Mg or SmtolueneOOHHO第9页/共90页第十页，共90页。3 3、Grinard Grinard 反应反应(fnyng)(fnyng)XRMgetherRMgXRRORRRMgX+OHR第10页/共90页第十一页，共90页。4 4、Reformatsky Reformatsky 反应反应(fnyng)(fnyng)ZnetherOEtROXOEtROXZnRRORROHOEtRO第11页/共90页第十二页，共90页。5 5、Barbier Barbier 反应反应(fnyng)(fny

3、ng)ROR+BrMetalH2OROHRM = Bi Al In Sm Sn 第12页/共90页第十三页，共90页。金属钐参与金属钐参与(cny)的有的有机反应机反应第13页/共90页第十四页，共90页。LnICH2CH2I+THFLnI2+CH2CH2Ln=Sm, Ybn-C7H15CHOn-C12H25In-C12H25OTsSmI22SmI22SmI22n-C7H15CH2OHn-C12H26n-C12H26n-C4H9ISmI22+n-C6H13COCH3n-C6H13Cn-C4H9CH3OHKagan:第14页/共90页第十五页，共90页。PhCH2BrPhCH2CHCH2OSmI

4、22SmI22PhCH2CH2PhPhCH2CHCH2ONSmI221),THF2) H O3+ONH2第15页/共90页第十六页，共90页。RXSm2+RX-+Sm3+.Possible Mechanism:RX-R X+.R Sm2+R+Sm3+R SH+RH+S.(Solvent)RSH+RH+S第16页/共90页第十七页，共90页。ORRSm2+CORR.+Sm3+CORR.+H+(or SH)COHRR.COHRR.+COHRRSm2+Sm3+COHRR+H+(or SH)RCOHHR第17页/共90页第十八页，共90页。RXR OOSmI2OHROSmI2RSmI2+SmI2SmI

5、2H+.R RXSmI2+SmI2XSmI2R +RSmI2+RSmI2OOSmI2ROHRH+第18页/共90页第十九页，共90页。第19页/共90页第二十页，共90页。PhCOCH2BrTHFSmI21.2.RCHOH O2HROPhHSynth. Commun. 1988, 18, 2003 PhCOCH2BrPhCOCH2BrPhCOCH2BrSmI2-SmI2BrCH2OPh.Sm(III)/I_BrOPhSm(III)I_I_IOPhSm(III)/I_IOPhSm(III)I_OSm(III)PhSmI2-IBr-I2第20页/共90页第二十一页，共90页。RXOR12+R CH

6、O3SmI3THFRORRH123X=Br, COCH3, COOCH3Tetrahedron Lett. 1993, 24, 4547 C6H5CCH2BrOorSmI3SmI2RCOClOOOHHCOOHC6H5OOC6H5ROOTetrahedron Lett., 1996, 37, 3885 第21页/共90页第二十二页，共90页。ArNO2ArNOArNOSmI2.ArNNROSmI2.SmI22I2SmOSmI2SmI2RCNSmI2ArNNROSmI2SmI2SmI22I2SmOSmI2ArNNRSmI2SmI2OH2ArNHRNHR NO2R CN+12SmI2(6 eq.),

7、 THF, r.t.2. 10%K2CO31. RNHRNH12J. Chem. Soc. Perkin Trans. 1, 1998, 2899mechanism第22页/共90页第二十三页，共90页。RN31+RCN22SmI2THF1./2.10% K2CO3RNHRNH12RN31SmI2N2RN1SmI2RCN2SmI2RNSmI22RN1SmI2H2ONHR2RN1H.RN2RN1SmI2.J. Chem. Res.(s), 2001, 32Yield: 60-72%第23页/共90页第二十四页，共90页。ROPh1ORPhROHOHROHRPhPh1211SmI2ROSm2Ph.

8、R CN2SmI2OSmI2RNSmI2PhR1H2O, HClROSmI1RPhPh11I2SmOH2O, HClH2O, HClC2ROPh1+RCNSmI22.2THF, refluxORPhROH+OHROHRPhPh111Tetrahedron Lett. 1998, 39, 8491第24页/共90页第二十五页，共90页。ArXPhZ_+SmI2THF-DMFArZPh+XPhZ =PhSe , PhCH Se , PhTe , PhS2_ArX=PhI, 1-BrPh, 1-BrAdm, 2-ClQuin_Heteroatom Chem. 2001, 12, 539 第25页/共

9、90页第二十六页，共90页。Chin. J. Chem. 2001, 19, 634 Yield: 70-85%cis:/trans 90/10-95/5第26页/共90页第二十七页，共90页。第27页/共90页第二十八页，共90页。ArNO2Sm/I2 (trace)THF-NH4ClArNH2+ArNHNHArSynlett, 1999, 1065RSSO3NaSm/Cat. I2THF, r.t.RSSRSynth. Commun., 1997, 27 ,1043RN3Sm/Cat. I2MeOH, N2, r.t. or refluxRNH2Tetrahedron Lett., 199

10、7, 27, 1065第28页/共90页第二十九页，共90页。Tetrahedron, 1999, 55, 10695 第29页/共90页第三十页，共90页。Chin. J. Chem. 2001, 19, 914 Only (E)-cinnamates (J=14-18Hz) (Z)-cinnamates (J=6-12Hz) was not detected第30页/共90页第三十一页，共90页。SO2PhCNSm/HOAc/EtOHArCHArCNArCHSO2PhORSm/HOAcArCH2ROArSO2PhSm/HOAcArHYield: 61-91%J. Chem. Res.(s)

11、, 2001, 26第31页/共90页第三十二页，共90页。Synth. Commun. 1995, 25, 1825 Synth. Commun. 1997, 27, 1428 J. Chem. Res(s), 1999, 214第32页/共90页第三十三页，共90页。RNO2+R2CN1.2.Sm/TiCl4, THF, reflux10%K2CO3RNHRNH21Yield: 52-81%Synth. Commun. 1998, 28, 3294 J. Chem. Res.(s), 2000, 472=60/4070/30第33页/共90页第三十四页，共90页。Heteroatom Ch

12、em. 1999, 10, 203 第34页/共90页第三十五页，共90页。Synth. Commun. 2001, 31, 47 Chin. J. Chem., 2001, 20, 202 第35页/共90页第三十六页，共90页。ArSO2ClRXArSO2R+Sm/NiCl2THF, 50-60 COSynth. Commun., 1997, 27, 2749,Ibid, 1999, 10, 899,Synth. Commun., 2002, 32, 189,第36页/共90页第三十七页，共90页。J. Chem. Res.(S) 1999, 280 Chin. Chem. Lett. 2

13、000, 11, 195 第37页/共90页第三十八页，共90页。Chin. J. Chem. 2000, 18, 69 mechanism第38页/共90页第三十九页，共90页。Synth. Commun. 2000, 30, 1731 Chin. Chem. Lett. 1999, 10, 729 J. Chem. Res.(S) 1999, 682 J. Chem. Res.(s) 2001, 160 Yield: 54-84%第39页/共90页第四十页，共90页。第40页/共90页第四十一页，共90页。SmI2SeSe2-Se2-RCOClArN2BF4RCOClSeCORRCOSeS

14、eCORRCOSeRCOSe CORSmI2ArZZArArZSmI22R COCl1ArZCOR1RXArZRXYCNArZYCNBtRNHCOPh1PhCONHCHZArR1Z=S, Se, Te. Y=CN, COOEtSynth. Commun., 1993, 23, 1403Synth. Commun., 1994, 24, 1339第41页/共90页第四十二页，共90页。J.Chen. Res., 1998, 6, 350ArCOCH2BrRSeBrSmI2SmI3orCH3CNArCOCH2SeR+ArSeSiMe3SmI2/THFreflux, 3hArSeSmI2RXrefl

15、ux, 3hArSeRSynth. Commun., 1996, 26, 1517BtRNR R12 3R SeSeRSmI244RNR RSeR12 34Synth. Commun., 1996, 26, 3277BtCH2ClRSSO3Na + SmI2RSSmI22RSSR + SmI2RSSmI222BtCH2SRSynth. Commun., 1998, 28, 2657NNNBt=第42页/共90页第四十三页，共90页。PhSeSePhSm/TMSCl/H2OPhSe_Rz3PhSeRz3OR2PhSeROH2R X1PhSeR1J.Chem. Res. (s), 1998, 59

16、8Z=CN, COOMe第43页/共90页第四十四页，共90页。ArCOCH2Br+RSeBrorSmI3SmI2CH3CNArCOCH2SeBrArC=CH2O SmI2 Synth. Commun. 1996, 26, 1417 RSCNSmI2SmI22RSSRRSSmI2RCOClRSCROTetrahedron Lett., 1994, 15, 8833 BtCH2ClRTeTeRBtCH2TeRNNNBt=SmI2RSeSeRBtCH2SeRSmI2Synth. Commun. 1996, 26, 3283 第44页/共90页第四十五页，共90页。第45页/共90页第四十六页，共9

17、0页。Chin. J. Chem., 1999, 1, 1第46页/共90页第四十七页，共90页。Synth. Comm., 1997, 27, 1495CN+SmBrTHFNH2第47页/共90页第四十八页，共90页。The Synthesis of N-(1-allyl-3-butenyl)-N-Aryl Amine by Addition of Organosamarium Reagent to FormanilideJ. Chem. Res. (s), 2001, in press第48页/共90页第四十九页，共90页。mechanism第49页/共90页第五十页，共90页。The r

18、eaction of acyclic amides with allylsamarium bromideTetrahedron Lett. 2001, 42, 8507第50页/共90页第五十一页，共90页。Direct Construction of Quaternary Carbon Centre Utilizing an Organosamarium Reagent Tetrahedron Lett. 2001, 42 8507第51页/共90页第五十二页，共90页。mechanism第52页/共90页第五十三页，共90页。The reactions of o-phthalimide a

19、nd succinimide with allylsamarium bromide第53页/共90页第五十四页，共90页。Samarium Induced Allylation of Lactones A Facile Synthesis of 2,2-Diallylated Cyclicethers 第54页/共90页第五十五页，共90页。The reaction of maleic anhydride with allylsamarium bromide第55页/共90页第五十六页，共90页。第56页/共90页第五十七页，共90页。Tetrahedron Lett. 1997, 38, 8

20、063 ArRCNCO2RNH2ROOCNCCOORArArSmI2THF, r.t.10min第57页/共90页第五十八页，共90页。ArCHCCNCOORSmI2ArCHCCNCOOR-.COORCOORCNCNArAr.-protonationNHROOCNCCOORArArNH2ROOCNCCOORArArNROOCNCCOORArAr-SmI2-11mechanism第58页/共90页第五十九页，共90页。第59页/共90页第六十页，共90页。Reductive Cyclization of Arylmethylidenemalononitrile Promoted by SmI2A

21、rHCNCNNH2NCNCCNArArSmI2THF, r.t.5min1RRXNO2CNSmI2(6 eq.), THF, r.t.2. 10%K2CO31. NRRXNH2122J. Chem. Soc. Perkin Trans 1, 1998, 2899J. Chem. Soc. Perkin Trans 1, 1998, 2399 第60页/共90页第六十一页，共90页。ArRCNCNArRArRNH2CNCNCNRArArRNH2CNCNCNSmTHF-NH4Cl (aq)+ArHCNCO2C2H5SmTHF-NH4Cl (aq)HArArHNH2CNCO2C2H5CO2C2H5+

22、other isomersmajorminorTetrahedron Lett. 1998, 39,5257Tetrahedron 1999, 55,10695Reductive Coupling of 1,1-Dicyanoalkenes Promoted by Metallic Samarium in Aqueous MediaMetallic Samarium Promoted Reductive Dimerization Cyclization of gem-diactivated Alkenes第61页/共90页第六十二页，共90页。第62页/共90页第六十三页，共90页。ArRNH

23、CNArRNCCNArRNCCNHArRArRNH2CNCNCNArRNCCNRArNCCNNCNCRArArRNHCNArRNCCNArRNCCNHRArArRNH2CNCNCNArCNCNRArRNCNCArRCNCNArRCNCNArRCNCN_H+tonation3.tautomerization_H+tonation3.tautomerization_e_.coupling第63页/共90页第六十四页，共90页。ArRCNCNArRArRNH2CNCNCNRArArRNH2CNCN

24、CNSm/TMSCl/THF/H2O(trace)H2O quenching+(cis)(trans)ArRCNCNArRCNCNSET_.couplingRArArRCNCNCNNSm(III)_cyclizationRArArRNCNCN_Sm(III)1.protonation2.tautomerizationArRArRNH2CNCNCNRArArRNH2CNCNCNArRArRCNCNCNNSm(III)_cyclizationArRArRNCNCN_Sm(III)1.protonation2.tautomerizationTetrahedron 1998, 54,11129第64页

25、/共90页第六十五页，共90页。ArCHArOSmI21.2THF, r.t.ArArOHArOArSynth. Commun, 2000, 30(4), 597 第65页/共90页第六十六页，共90页。OOPhPh+RCNSmI24THF, refluxNHRPhPhOCNSmI22.2THF, reflux78%OOHOPhCNSmI22.2THF, reflux85%OHOPh第66页/共90页第六十七页，共90页。NH2OHArNCArHCHCH2CArArOCH(CN)2SmI22.2THF, reflux1221NH2ArOHNCArH21CHCH2CArArOCH(CN)212S

26、mI2CHCH2CArArOSmI2CHNCN12.NSmI2ArOSmI2NCAr21NSmI2ArOSmI2NCAr21NH2OHArNCArH21NH2ArOHNCArH21+SmI2H2O, HClSynthesis, 2000, (1), 91 第67页/共90页第六十八页，共90页。Intramolecular Ketone-ester Reductive Coupling Reactions Promoted by SmI2Tetrahedron Lett. 2001, 42, 5745第68页/共90页第六十九页，共90页。NH2OHArNCArHCHCH2CArArOCH(C

27、N)2TiCl4/SmTHF, r.t.1221NH2ArOHNCArH21+NH2NCArAr21+CHCH2CArArOCH(CN)212MCHCH2CArArOMCHNCN12.NMArOMNCAr21NMArOMNCAr21NH2OHArNCArH21NH2ArOHNCArH21+MNH2NCArAr21加 热低 温Tetrahedron, 2000, 56, 2953 Intramolecular Ketone-nitrile Reductive Coupling Reactions Promoted by Sm/TiCl4 System第69页/共90页第七十页，共90页。Chin

28、. Chem. Lett. , 2000,11(5), 389Synthesis of 3,4-dihydro-(2H)-1,2,4-benzothiadiazine-1,1-dioxides Promoted by SmI2第70页/共90页第七十一页，共90页。Chin. Chem. Lett., 2000, 11(5), 387Simultaneous Reduction of Nitro Group and S-S Bond in Nitrodisulfides by SmI2: A New Approach to Benzothiazolines第71页/共90页第七十二页，共90页

29、。J. Indian Chem. Soc., 2001, 78, 314SmI2 Promoted Reductive Cyclization of Nitrodisulfides with Nitriles: A New Route to Benzothiazoles第72页/共90页第七十三页，共90页。Heteroatom Chem., 2001, 12(3), 156.Synthesis of 2H-1,4-benzothiazines Promoted by SmI2第73页/共90页第七十四页，共90页。J. Chem. Res (s), 2000, 386A New Route

30、ot 2,3-dihydro-1,5-benzothiazepines第74页/共90页第七十五页，共90页。Synthesis of 3-cyano-2,3-diydro-1,5-benzothiazepin-4(5H)-ones Promoted by SmI2Synth. Comm., in press第75页/共90页第七十六页，共90页。Tetrahedron Lett., 2001, 42, 3125Synthesis of 2H-1,4-benzothiazin-3(4H)-ones and 2H-1,4-benzoselenazin-3(4H)-ones with the Ai

31、d of SmI2第76页/共90页第七十七页，共90页。Chin. J. Chem., 2000,18(5), 786Synthesis of 3,4-dihydro-(2H)-1,2,4-benzothiadiazine-1,1-dioxides 第77页/共90页第七十八页，共90页。Synthesis of 2,3-dihydro-1H-1,5-benzodiazepinesXN3NO2XN2-N2- NNXSMeArTiCl4/SmArCCHSMeSMeOYield: 78-85%Chin. J. Chem. 2001, 19, 996 第78页/共90页第七十九页，共90页。Tet

32、rahedron Lett. 2001, 42, 73Simultaneous Reduction of the Nitro Group and the azide Group in o-nitrophenylazide Induced by Sm/TiCl4 System: Synthesis of 2,3-dihydro-1H-1,5-benzodiazepines第79页/共90页第八十页，共90页。第80页/共90页第八十一页，共90页。A Novel Reduction of Nitrophenoxy Compounds Promoted by Sm/TiCl4 System: An