有机合成化学PPT课件

1、第1页/共90页MediatePromoteCatalyst第2页/共90页活泼金属参与的有机反应活泼金属参与的有机反应第3页/共90页第4页/共90页1 1、还原反应、还原反应NO2RNH2RMetalH+M = Zn Fe Sn 第5页/共90页RRRRNaNH3(l)第6页/共90页RRORROH+Zn-HgClaimenson Reduction第7页/共90页RRRRBrBrRRRRZn第8页/共90页2 2、还原偶联反应、还原偶联反应Mg or SmtolueneOOHHO第9页/共90页3 3、Grinard 反应反应XRMgetherRMgXRRORRRMgX+OHR第10页/

2、共90页4 4、Reformatsky 反应反应ZnetherOEtROXOEtROXZnRRORROHOEtRO第11页/共90页5 5、Barbier 反应反应ROR+BrMetalH2OROHRM = Bi Al In Sm Sn 第12页/共90页金属钐参与的有机反应金属钐参与的有机反应第13页/共90页E0 aq Sm3+/Sm2+ = -1.55VLnICH2CH2I+THFLnI2+CH2CH2Ln=Sm, Ybn-C7H15CHOn-C12H25In-C12H25OTsSmI22SmI22SmI22n-C7H15CH2OHn-C12H26n-C12H26n-C4H9ISmI22

3、+n-C6H13COCH3n-C6H13Cn-C4H9CH3OHKagan:第14页/共90页PhCH2BrPhCH2CHCH2OSmI22SmI22PhCH2CH2PhPhCH2CHCH2ONSmI221),THF2) H O3+ONH2第15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ORRSm2+CORR.+Sm3+CORR.+H+(or SH)COHRR.COHRR.+COHRRSm2+Sm3+COHRR+H+(or SH)RCOHHR第1

4、7页/共90页RXR OOSmI2OHROSmI2RSmI2+SmI2SmI2H+.R RXSmI2+SmI2XSmI2R +RSmI2+RSmI2OOSmI2ROHRH+第18页/共90页SmISmI2 2、SmISmI3 3促进的有机反应促进的有机反应第19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_O

5、Sm(III)PhSmI2-IBr-I2第20页/共90页RXOR12+R CHO3SmI3THFRORRH123X=Br, COCH3, COOCH3Tetrahedron Lett. 1993, 24, 4547 C6H5CCH2BrOorSmI3SmI2RCOClOOOHHCOOHC6H5OOC6H5ROOTetrahedron Lett., 1996, 37, 3885 第21页/共90页ArNO2ArNOArNOSmI2.ArNNROSmI2.SmI22I2SmOSmI2SmI2RCNSmI2ArNNROSmI2SmI2SmI22I2SmOSmI2ArNNRSmI2SmI2OH2Ar

6、NHRNHR NO2R CN+12SmI2(6 eq.), THF, r.t.2. 10%K2CO31. RNHRNH12J. Chem. Soc. Perkin Trans. 1, 1998, 2899mechanism第22页/共90页RN31+RCN22SmI2THF1./2.10% K2CO3RNHRNH12RN31SmI2N2RN1SmI2RCN2SmI2RNSmI22RN1SmI2H2ONHR2RN1H.RN2RN1SmI2.J. Chem. Res.(s), 2001, 32Yield: 60-72%第23页/共90页ROPh1ORPhROHOHROHRPhPh1211SmI2R

7、OSm2Ph.R CN2SmI2OSmI2RNSmI2PhR1H2O, HClROSmI1RPhPh11I2SmOH2O, HClH2O, HClC2ROPh1+RCNSmI22.2THF, refluxORPhROH+OHROHRPhPh111Tetrahedron Lett. 1998, 39, 8491第24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 SRN1 React

8、ion of Haloarenes with Benzenethiolate, Benzeneselenolate, and Benzenetellurolate ions Promoted by SmI2第25页/共90页ArC ClOSmI2CH3CNArCO2O2CArArAr12 CBAOOO C ArArArCO C ArCArCOCl2.CCArArOOCCArArOOSm I_.SmI22-Sm ISmI2Ar CO.Ar CO-2Ar COClSmI2SmI2Ar CC ArOOChin. J. Chem. 2001, 19, 634 Yield: 70-85%cis:/tra

9、ns 90/10-95/5第26页/共90页金属钐金属钐/ /辅助试剂促进的有机反应辅助试剂促进的有机反应第27页/共90页ArNO2Sm/I2 (trace)THF-NH4ClArNH2+ArNHNHArSynlett, 1999, 1065Sm/I2 (cat)体系RSSO3NaSm/Cat. I2THF, r.t.RSSRSynth. Commun., 1997, 27 ,1043RN3Sm/Cat. I2MeOH, N2, r.t. or refluxRNH2Tetrahedron Lett., 1997, 27, 1065第28页/共90页 RSSR SmTHF-NH4Cl (aq.

10、)RSSO3Na SmTHF-NH4Cl (aq.)BrBrCC1R2R3RR41R2R3RR4Tetrahedron, 1999, 55, 10695 Sm/NH4Cl体系第29页/共90页Sm/HOAc体系ArCO2RTHFSm/HOAcArCHOPhSO2CH2CO2RCO2RArCHCSO2Ph+75-86%BenzenePiperidine1234Chin. 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SO2PhCNS

11、m/HOAc/EtOHArCHArCNArCHSO2PhORSm/HOAcArCH2ROArSO2PhSm/HOAcArHYield: 61-91%J. Chem. Res.(s), 2001, 26第31页/共90页 PhSOCH3PhSCH3Sm/Cp2TiCl2 R CH=NR122R1R HNNHR22R1Sm/Cp2TiCl2Synth. Commun. 1995, 25, 1825 Synth. Commun. 1997, 27, 1428 ArSO2XArSSArX=Cl, Br, NaSm/Cp2TiCl2THF, refluxJ. Chem. Res(s), 1999, 21

12、4Sm/Cp2TiCl2 体系第32页/共90页Sm/TiCl4 体系RNO2+R2CN1.2.Sm/TiCl4, THF, reflux10%K2CO3RNHRNH21Yield: 52-81%Synth. Commun. 1998, 28, 3294 ArSO2CHBr2+12R COR12ArSO2CH=CR R123 ( E/Z )Sm/SmI2/TiCl4(cat.)THFJ. Chem. Res.(s), 2000, 472=60/4070/30第33页/共90页Heteroatom Chem. 1999, 10, 203 RSeSmCl2 Sm/HgCl211RSeCORR CO

13、ClRSeSeR3RSeCO2RR X4RSeR4OR5RSeOHR5ZR66RSeRZ3ClCO2R2(R CO)2O 2RSeCORSm/HgCl2 体系第34页/共90页 ArSO2CHBr2+R COR12ArSO2CH=CR R12Sm/SmI2/CrCl3(cat.)THFSynth. Commun. 2001, 31, 47 PhTeTePhSm/CrCl3(cat.)/THF PhTe _R COTePh1PhTeCH(R )CH(R )X 43PhTeR 2R X2R CH=C(R )X34R COCl1Chin. J. Chem., 2001, 20, 202 Sm/CrC

14、l3 体系第35页/共90页 ArSO2ClArSSArSm/NiCl2/cat. KI60 , 3hCArSO2ClRXArSO2R+Sm/NiCl2THF, 50-60 CO RN3Sm/CoCl2 6H2O.RNH2THF, r.t.R=alkyl, aryl, aroyl, arylsulfonylSynth. Commun., 1997, 27, 2749,Ibid, 1999, 10, 899,Synth. Commun., 2002, 32, 189,第36页/共90页J. Chem. Res.(S) 1999, 280 Chin. Chem. Lett. 2000, 11, 1

15、95 CH2=CHCH2Br+RYYRCH2=CHCH2YRY=Se, STHF-H2OSm/BiCl3+1BrCH2CO2RR (R )NCH(R )CH2CO2R1234NBt R RR234THF/H2OSm/BiCl3Sm/BiCl3 体系第37页/共90页Chin. J. Chem. 2000, 18, 69 BrCH2CO2R + R ZZRSm/SbCl3DMF/H2OR ZCH2CO2R Y=Se, S12122Sm/SbCl3 体系SbBr3Sm(0)SmBr3SmCl3Sm(0)Sb(0)SbCl3R Br1R nSbBr3-n1R SeSeR22R SeR21R Br1R

16、 SeR21R : PhCH2, CH2=CHCH212(R Se)nSbBr3-nmechanism第38页/共90页Synth. Commun. 2000, 30, 1731 Chin. Chem. Lett. 1999, 10, 729 J. Chem. Res.(S) 1999, 682 RSeSeRR CH=CHCH2Br1R CH=CHCH2SeR1Sm/CdCl2DMF/H2O+Sm/CdCl2THF/H2OCOCH2BrCOCH2CH(OH)RRCHONHRBtR 12+RSSO3NaR NH(R )CHSR12THF H2O, air, r.t.Sm/ZnCl2R1SeSeR

17、1+R2XSm/ZnCl2DMF H2OR1SeR2(R1: Aryl, Alkyl R2X: ClCH2CN, BrCH2CO2Et, PhCH2Br)J. Chem. Res.(s) 2001, 160 Yield: 54-84%第39页/共90页钐试剂用于合成钐试剂用于合成S S、SeSe、TeTe杂原子化合物杂原子化合物第40页/共90页SmI2SeSe2-Se2-RCOClArN2BF4RCOClSeCORRCOSeSeCORRCOSeRCOSe CORSmI2ArZZArArZSmI22R COCl1ArZCOR1RXArZRXYCNArZYCNBtRNHCOPh1PhCONHCH

18、ZArR1Z=S, Se, Te. Y=CN, COOEtSynth. Commun., 1993, 23, 1403Synth. Commun., 1994, 24, 1339第41页/共90页J.Chen. Res., 1998, 6, 350ArCOCH2BrRSeBrSmI2SmI3orCH3CNArCOCH2SeR+ArSeSiMe3SmI2/THFreflux, 3hArSeSmI2RXreflux, 3hArSeRSynth. Commun., 1996, 26, 1517BtRNR R12 3R SeSeRSmI244RNR RSeR12 34Synth. Commun., 1

19、996, 26, 3277BtCH2ClRSSO3Na + SmI2RSSmI22RSSR + SmI2RSSmI222BtCH2SRSynth. Commun., 1998, 28, 2657NNNBt=第42页/共90页PhSeSePhSm/TMSCl/H2OPhSe_Rz3PhSeRz3OR2PhSeROH2R X1PhSeR1J.Chem. Res. (s), 1998, 598Z=CN, COOMe第43页/共90页ArCOCH2Br+RSeBrorSmI3SmI2CH3CNArCOCH2SeBrArC=CH2O SmI2 Synth. Commun. 1996, 26, 1417

20、RSCNSmI2SmI22RSSRRSSmI2RCOClRSCROTetrahedron Lett., 1994, 15, 8833 BtCH2ClRTeTeRBtCH2TeRNNNBt=SmI2RSeSeRBtCH2SeRSmI2Synth. Commun. 1996, 26, 3283 第44页/共90页烯丙基溴化钐在有机合成中的应用烯丙基溴化钐在有机合成中的应用第45页/共90页CH2CHCH2Br CH2CHCH2SmBr Sm/THFRZZRRZNCXX=S,ONHXCNHRRR 123R CHNR R12 3CH NRRBtR 123CRRNR123RCH(OAc)2RCHOAcR

21、 CHCHCRO12R CHCHCROH21RCRO12CRROH12CHNCORRRCl12RCHNCORR12Z=S, SeZ=S,Se Allylsamarium bromide induced monoallylation reactionsChin. J. Chem., 1999, 1, 1第46页/共90页Synth. Comm., 1997, 27, 1495CN+SmBrTHFNH2The synthesis of Homoallylamines by the addition of organosamarium reagent to nitriles第47页/共90页The

22、Synthesis of N-(1-allyl-3-butenyl)-N-Aryl Amine by Addition of Organosamarium Reagent to FormanilideRNHCHO+2SmBrTHFr.t.RNHCHJ. Chem. Res. (s), 2001, in press21CH2CHCH2Br+SmTHFr.t.CH2CHCH2SmBrNHCHRTHFr.t.+SmBr2RNHCHO第48页/共90页NHCHORNHCHRSmBrOSmBr_HOSmBrNRCHSmBr1 )2 )H2ONHCHR1234mechanism第49页/共90页The r

23、eaction of acyclic amides with allylsamarium bromide2SmBrOOHTHFr.t.+NH2R1CNR2CR1NR2THFr.t.+2SmBrOHHTetrahedron Lett. 2001, 42, 8507第50页/共90页Direct Construction of Quaternary Carbon Centre Utilizing an Organosamarium Reagent SmBrSmBrBrNNO+2+SmTHFr.t.THFr.t.( )n( )nHHTetrahedron Lett. 2001, 42 8507第51

24、页/共90页EDCBAHN( )nHNO( )nSmBrHNOSmBr( )neliminating HOSmBrN( )nSmBrN( )nSmBrH2Omechanism第52页/共90页The reactions of o-phthalimide and succinimide with allylsamarium bromideSmBrHminmin27654THF r.t.5NHOONHOOTHF r.t.5NONHO第53页/共90页Samarium Induced Allylation of Lactones A Facile Synthesis of 2,2-Diallylat

25、ed Cyclicethers +n = 1, 2, 3 ( )nOORSmBrSmBrBrOR2THFr.t.( )nR = H, CH3+SmTHF r.t.cat. I2第54页/共90页The reaction of maleic anhydride with allylsamarium bromideTHFr.t.SmBrOOOO+第55页/共90页钐试剂促进的环化反钐试剂促进的环化反应应第56页/共90页Tetrahedron Lett. 1997, 38, 8063 ArRCNCO2RNH2ROOCNCCOORArArSmI2THF, r.t.10minCyclodimeriaz

26、tion of Arylidenecyanoacetate Promoted by SmI2第57页/共90页ArCHCCNCOORSmI2ArCHCCNCOOR-.COORCOORCNCNArAr.-protonationNHROOCNCCOORArArNH2ROOCNCCOORArArNROOCNCCOORArAr-SmI2-11mechanism第58页/共90页第59页/共90页Reductive Cyclization of Arylmethylidenemalononitrile Promoted by SmI2ArHCNCNNH2NCNCCNArArSmI2THF, r.t.5m

27、in1RRXNO2CNSmI2(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ArRCNCNArRArRNH2CNCNCNRArArRNH2CNCNCNSmTHF-NH4Cl (aq)+ArHCNCO2C2H5SmTHF-NH4Cl (aq)HArArHNH2CNCO2C2H5CO2C2H5+other isomersmajorminorTetrahedron Lett. 1998

28、, 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62页/共90页mechanismArRNHCNArRNCCNArRNCCNHArRArRNH2CNCNCNArRNCCNRArNCCNNCNCRArArRNH

29、CNArRNCCNArRNCCNHRArArRNH2CNCNCNArCNCNRArRNCNCArRCNCNArRCNCNArRCNCN_H+tonation3.tautomerization_H+tonation3.tautomerization_e_.coupling第63页/共90页Water Accelerated Sm/TMSCl System: Reductive Dimerization Cyclization of 1,1-dicyanoalkenesArRCNCNArRArR

30、NH2CNCNCNRArArRNH2CNCNCNSm/TMSCl/THF/H2O(trace)H2O quenching+(cis)(trans)ArRCNCNArRCNCNSET_.couplingRArArRCNCNCNNSm(III)_cyclizationRArArRNCNCN_Sm(III)1.protonation2.tautomerizationArRArRNH2CNCNCNRArArRNH2CNCNCNArRArRCNCNCNNSm(III)_cyclizationArRArRNCNCN_Sm(III)1.protonation2.tautomerizationTetrahed

31、ron 1998, 54,11129第64页/共90页ArCHArOSmI21.2THF, r.t.ArArOHArOArSynth. Commun, 2000, 30(4), 597 Cyclodimerization of , -unsaturated Ketones Promoted by SmI2第65页/共90页SmI2 Promoted Intramolecular Ketone-nitrile Reductive Coupling ReactionsOOPhPh+RCNSmI24THF, refluxNHRPhPhOCNSmI22.2THF, reflux78%OOHOPhCNS

32、mI22.2THF, reflux85%OHOPh第66页/共90页NH2OHArNCArHCHCH2CArArOCH(CN)2SmI22.2THF, reflux1221NH2ArOHNCArH21CHCH2CArArOCH(CN)212SmI2CHCH2CArArOSmI2CHNCN12.NSmI2ArOSmI2NCAr21NSmI2ArOSmI2NCAr21NH2OHArNCArH21NH2ArOHNCArH21+SmI2H2O, HClSynthesis, 2000, (1), 91 第67页/共90页Intramolecular Ketone-ester Reductive Coup

33、ling Reactions Promoted by SmI2R CHCH2CH(CO2Et)2CRO12SmI2 (2.2 mmol)THFOCO2EtRRHO12+OCO2EtRR12312R CHCH2CH(CO2Et)2CRO12SmI2R CHCH2CHCO2EtCRCO2EtOSmI212.SmI2OSmI2ROSmI2OEtEtO2CR121ABCOSmI2REtO2CRO12H2O, HClOHREtO2CRO122EtOSmI2Tetrahedron Lett. 2001, 42, 5745第68页/共90页NH2OHArNCArHCHCH2CArArOCH(CN)2TiCl

34、4/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_O(SmI2)21SO2N(R )SmI

35、2NHSmI2O2HR2R1NNS2R CHON(SmI2)2SO2NHR1SO2NHR1NO2SmI2/THF, r.t.221RNHNSO2RI2SmOSmI2R CHO1NHSmI2SO2N(R ) SmI21N(SmI2)2SO2NHRI2SmOSmI24 SmI21NOSO2NHR1NO2SO2NHRI2SmOSmI22 SmI2Chin. 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1RN

36、SRH21 R COR O(SmI2)2_XSSmI2N(SmI2)2THF, r.t.NO2S )2SmI2/HMPAXXX = H or ClChin. Chem. Lett., 2000, 11(5), 387XN(SmI2)2SSmI2SmI2THF/r.t.XNO2S )2XNSRTHF, r.t.R COZSimultaneous Reduction of Nitro Group and S-S Bond in Nitrodisulfides by SmI2: A New Approach to Benzothiazolines第71页/共90页XX2r.t.SmI2/THFRCN

37、+S )NO2RNS.C NNSRN(SmI2)32 SmI2I2SmOSmI2RSmI2NSN(SmI2)2 N(SmI2)2NSOSmI2R SmI2ROSmI2NSSmI2 RCN.NOSmI2SSmI2 SmI2SSmI2 NOI2SmOSmI23 SmI21/2NO2S )2J. Indian Chem. Soc., 2001, 78, 314SmI2 Promoted Reductive Cyclization of Nitrodisulfides with Nitriles: A New Route to Benzothiazoles第72页/共90页THF, r.t.XNO2S

38、 )2THF/r.t.SmI2XN(SmI2)2SSmI2NSRXRC CH2BrOHeteroatom Chem., 2001, 12(3), 156.XNO2S )2SmI2/THFr.t.XN(SmI2)2SSmI2XNSORHRCH(Y)ZXNH2SHMeOHRCH(Y)ZX = H, Cl; R = H, alkyl, aryl; Z = CO2H, CO2Me, CO2Et, CN Y=H, BrSynthesis of 2H-1,4-benzothiazines Promoted by SmI2第73页/共90页r. t.XNSRArArC HCHCROXN(SmI2)2SSmI

39、2r. t.SmI2/T HFXNO2S )2J. Chem. Res (s), 2000, 386A New Route ot 2,3-dihydro-1,5-benzothiazepines第74页/共90页0THF, 60 CHXNSOCNArArCHC(CN)2THF, r.t.SmI2/HMPAN(SmI2)2SSmI2XNO2S )2XProtonationXNSSmI2NArCNHSmI2SmI2HXNSOCNArCNArCNHSmI2N(SmI2)2SX0THF, 60 CArCH C(CN)2THF, r.t.SmI2/HMPAN(SmI2)2SSmI2XNO2S )2XSy

40、nthesis of 3-cyano-2,3-diydro-1,5-benzothiazepin-4(5H)-ones Promoted by SmI2Synth. Comm., in press第75页/共90页RCH(Y)ZHNSeORXXN(S mI2)2SeS mI2r.t.SmI2/THFXNO2Se )2Tetrahedron Lett., 2001, 42, 3125Synthesis of 2H-1,4-benzothiazin-3(4H)-ones and 2H-1,4-benzoselenazin-3(4H)-ones with the Aid of SmI2第76页/共9

41、0页r.t.21XNHNHSO2RRTiCl4/Sm, THF21R CORNO2SO2NH2X+ Ti (low-valent titanium reagent )refluxTHFSm + TiCl42RR1HNNHSO2R12RN CR (R )21SO2NH2OTiOTi2 Ti=O+-O2NNH2SH2O21R COR . Ti NOTiSO2NH2 Ti NOSO2NH2 Ti =O Ti NO2SO2NH2Chin. J. Chem., 2000,18(5), 786Synthesis of 3,4-dihydro-(2H)-1,2,4-benzothiadiazine-1,1-

42、dioxides 第77页/共90页2121R CHCHCORNNHRR-2-2NNTHF, r.t.Sm/TiCl4NO2N3Synthesis 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0 Ti 0NNRCH3R60 C, 2-5hRCCH3O-2-2NNTHF, r.t. NO2N30 Ti reflux, 2 hTHFSmTiCl4H+THFRCCH3ONH2NH2MeO

43、H5-10 minCH3CH2CCH2CH3ONNCH2CH3CH3CH2CH3CH2CH3H28m, yield = 53%O( )nNNH( )n( )n28k, n = 1, yield = 45%28l, n = 2, yield = 37%0THF, 60 C, 6-8 h0THF, 60 C, 4 hNN2-2-Tetrahedron Lett. 2001, 42, 73Simultaneous Reduction of the Nitro Group and the azide Group in o-nitrophenylazide Induced by Sm/TiCl4 Sys

44、tem: Synthesis of 2,3-dihydro-1H-1,5-benzodiazepines第79页/共90页1,5-H transferNNRCH3RHNHNCH2RCH3RNNCH3RCH3R2 Ti = O22NN Ti + Ti +0 Ti NH+N-RCH3RRCCH3ONO2N3N2, 2 Ti = O0 Ti reflux, 2 hTHFSmTiCl4+mechanism第80页/共90页A Novel Reduction of Nitrophenoxy Compounds Promoted by Sm/TiCl4 System: An Access to 2H-1,

45、4-benzoxazine DerivativesJ. Chem. Res(s). 2000, 385XOCHR1COC6H4R2NO2Sm/TiCl4THF, r.t., 10minNOC6H4RXR12Sm/TiCl4THF, r.t., 10minNORC6H4R2XRRORRNO211234第81页/共90页Synthesis of Dihydrofurans from Diaryl Ketones and Chalcones Promoted by SmI2/SmSynthesis 2001, 7, 1004R1COR2R3CH=CHCOR4+SmI2/Sm20min, r.t.OR

46、RRR2341SmR1COR2SmI2RCROSmI2R3CH=CHCOR4RCROSmI2R3CHCHCOR4RCOSmI2RR3CHCHCORRCOSmIRR3CHCHCORRCORSmIOR3CHCHCRORRRR.NOTO,I,Sm12121241241241234.第82页/共90页Convenient Preparation of Polysubstituted 3H-pyrroles Promoted by SmI2J. Chem. Soc. Perkin 1 2001, 2836C6H5CNArArCNSmI2,THFrefluxNH2ArNC6H5Ar123RRRR2CArCN.ArCNC6H5ArNprotonationtautomerization3NH2ArNC6H5ArRRRRRRR1ABTHFArCNC6H5SmI2ArCNC6H5.-ArCN.C6H5DSmI2cyclizationSmI2cyclizationSmI2ArCNC6H5ArNArC6H5ArNNSmI2ArC6H5ArNN1.2.ArC6H5ArNNSmI2Dmechanism第83页/共90页Synthesis of Polysubstituted Cyclopentenamines by SmI2 Yield: 63-79%Yield: 63-81%Y