有机合成化学.pptx

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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M=Zn Fe Sn 第5页/共90页第6页/共90页Claimenson Reduction第7页/共90页第8页/共90页2 2、还原偶联反应、还原偶联反应第9页/共90页3 3、Grinard 反应反应第10页/共90页4 4、Reformatsky 反应反应第11页/共90页5 5、Barbier 反应反应M=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9

2、0页E0 aq Sm3+/Sm2+=-1.55VKagan:第14页/共90页第15页/共90页Possible Mechanism:第16页/共90页第17页/共90页第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Synth.Commun.1988,18,2003 第20页/共90页Tetrahedron Lett.1993,24,4547 Tetrahedron Lett.,1996,37,3885 第21页/共90页J.Chem.Soc.Perkin Trans.1,1998,2899mechanism第22页/共90页J.Chem

3、.Res.(s),2001,32Yield:60-72%第23页/共90页Tetrahedron Lett.1998,39,8491第24页/共90页Heteroatom Chem.2001,12,539 SRN1 Reaction of Haloarenes with Benzenethiolate,Benzeneselenolate,and Benzenetellurolate ions Promoted by SmI2第25页/共90页Chin.J.Chem.2001,19,634 Yield:70-85%cis:/trans 90/10-95/5第26页/共90页金属钐金属钐/辅助试剂

4、促进的有机反应辅助试剂促进的有机反应第27页/共90页Synlett,1999,1065Sm/I2(cat)体系Synth.Commun.,1997,27,1043Tetrahedron Lett.,1997,27,1065第28页/共90页Tetrahedron,1999,55,10695 Sm/NH4Cl体系第29页/共90页Sm/HOAc体系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Yield:61-91%J.Chem.Res.

5、(s),2001,26第31页/共90页Synth.Commun.1995,25,1825 Synth.Commun.1997,27,1428 J.Chem.Res(s),1999,214Sm/Cp2TiCl2 体系第32页/共90页Sm/TiCl4 体系Yield:52-81%Synth.Commun.1998,28,3294 J.Chem.Res.(s),2000,472=60/4070/30第33页/共90页Heteroatom Chem.1999,10,203 Sm/HgCl2 体系第34页/共90页Synth.Commun.2001,31,47 Chin.J.Chem.,2001,2

6、0,202 Sm/CrCl3 体系第35页/共90页Synth.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.2000,11,195 Sm/BiCl3 体系第37页/共90页Chin.J.Chem.2000,18,69 Sm/SbCl3 体系mechanism第38页/共90页Synth.Commun.2000,30,1731 Chin.Chem.Lett.1999,10,729 J.Chem.Res.(S)1999,6

7、82 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Synth.Commun.,1993,23,1403Synth.Commun.,1994,24,1339第41页/共90页J.Chen.Res.,1998,6,350Synth.Commun.,1996,26,1517Synth.Commun.,1996,26,3277Synth.Commun.,1998,28,2657第42页/共90页J.Chem.Res.(s),1998,598Z=CN,COOMe第4

8、3页/共90页Synth.Commun.1996,26,1417 Tetrahedron Lett.,1994,15,8833 Synth.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Allylsamarium bromide induced monoallylation reactionsChin.J.Chem.,1999,1,1第46页/共90页Synth.Comm.,1997,27,1495The synthesis of Homoallylamines by the addition of or

9、ganosamarium reagent to nitriles第47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mechanism第49页/共90页The reaction of acyclic amides with allylsamarium bromideTetrahedron Lett.2001,42,8507第50页/共90页Direc

10、t Construction of Quaternary Carbon Centre Utilizing an Organosamarium Reagent Tetrahedron Lett.2001,42 8507第51页/共90页mechanism第52页/共90页The reactions of o-phthalimide and succinimide with allylsamarium bromide第53页/共90页Samarium Induced Allylation of Lactones A Facile Synthesis of 2,2-Diallylated Cycli

11、cethers 第54页/共90页The reaction of maleic anhydride with allylsamarium bromide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 Cyclodimeriaztion of Arylidenecyanoacetate Promoted by SmI2第57页/共90页mechanism第58页/共90页第59页/共90页Reductive Cyclization of Arylmethylidenemalononitrile Promote

12、d by SmI2J.Chem.Soc.Perkin Trans 1,1998,2899J.Chem.Soc.Perkin Trans 1,1998,2399 第60页/共90页Tetrahedron 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-d

13、iactivated Alkenes第61页/共90页第62页/共90页mechanism第63页/共90页Water Accelerated Sm/TMSCl System:Reductive Dimerization Cyclization of 1,1-dicyanoalkenesTetrahedron 1998,54,11129第64页/共90页Synth.Commun,2000,30(4),597 Cyclodimerization of,-unsaturated Ketones Promoted by SmI2第65页/共90页SmI2 Promoted Intramolecula

14、r Ketone-nitrile Reductive Coupling Reactions第66页/共90页Synthesis,2000,(1),91 第67页/共90页Intramolecular Ketone-ester Reductive Coupling Reactions Promoted by SmI2Tetrahedron Lett.2001,42,5745第68页/共90页Tetrahedron,2000,56,2953 Intramolecular Ketone-nitrile Reductive Coupling Reactions Promoted by Sm/TiCl4

15、 System第69页/共90页Chin.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J.Indian Che

16、m.Soc.,2001,78,314SmI2 Promoted Reductive Cyclization of Nitrodisulfides with Nitriles:A New Route to Benzothiazoles第72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J.Chem.Res(s),2000,386A New Route ot 2,3-dihydro-1,5-benzothiazepines第74页/共90页Synth

17、esis of 3-cyano-2,3-diydro-1,5-benzothiazepin-4(5H)-ones Promoted by SmI2Synth.Comm.,in press第75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 Aid of SmI2第76页/共90页Chin.J.Chem.,2000,18(5),786Synthesis of 3,4-dihydro-(2H)-1

18、,2,4-benzothiadiazine-1,1-dioxides 第77页/共90页Synthesis of 2,3-dihydro-1H-1,5-benzodiazepinesYield:78-85%Chin.J.Chem.2001,19,996 第78页/共90页Tetrahedron 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-1

19、H-1,5-benzodiazepines第79页/共90页mechanism第80页/共90页A Novel Reduction of Nitrophenoxy Compounds Promoted by Sm/TiCl4 System:An Access to 2H-1,4-benzoxazine DerivativesJ.Chem.Res(s).2000,385第81页/共90页Synthesis of Dihydrofurans from Diaryl Ketones and Chalcones Promoted by SmI2/SmSynthesis 2001,7,1004第82页/

20、共90页Convenient Preparation of Polysubstituted 3H-pyrroles Promoted by SmI2J.Chem.Soc.Perkin 1 2001,2836mechanism第83页/共90页Synthesis of Polysubstituted Cyclopentenamines by SmI2 Yield:63-79%Yield:63-81%Yield:55-90%第84页/共90页mechanism第85页/共90页Synthesis of Functionalized 2,3-Dihydrofuran by SmI2Yield:51-83%mechanism第86页/共90页Synthesis of Functionalized 2,3-Dihydropyrroles by SmI2第87页/共90页mechanism第88页/共90页J.Chem.Res.(s)2001,104 Yield:52-64%J.Chem.Res.(s)2001,394 Yield:72-84%CcChin.J.Chem.2001,19,616 第89页/共90页感谢您的观看。第90页/共90页