有机合成化学学习教案.pptx

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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。活泼金属参与活泼金属参与(cny)的有的有机反应机反应第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M=Zn Fe Sn 第5页/共90页第六页，共90页。第6页/共90页第七页，共90页。Claimenson Reduction第7页/共90页第八页，共90页。第8页/共90页第九页，共90页。2 2、还原、还原(hun yun

2、)(hun yun)偶联反应偶联反应第9页/共90页第十页，共90页。3 3、Grinard Grinard 反应反应(fnyng)(fnyng)第10页/共90页第十一页，共90页。4 4、Reformatsky Reformatsky 反应反应(fnyng)(fnyng)第11页/共90页第十二页，共90页。5 5、Barbier Barbier 反应反应(fnyng)(fnyng)M=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。E E0 aq0 aq Sm Sm3+3+/Sm/

3、Sm2+2+=-1.55V=-1.55VKagan:第14页/共90页第十五页，共90页。第15页/共90页第十六页，共90页。Possible Mechanism:第16页/共90页第十七页，共90页。第17页/共90页第十八页，共90页。第18页/共90页第十九页，共90页。SmI2SmI2、SmI3SmI3促进促进(cjn)(cjn)的有机反应的有机反应第19页/共90页第二十页，共90页。Synth.Commun.1988,18,2003 第20页/共90页第二十一页，共90页。Tetrahedron Lett.1993,24,4547 Tetrahedron Lett.,1996,3

4、7,3885 第21页/共90页第二十二页，共90页。J.Chem.Soc.Perkin Trans.1,1998,2899mechanism第22页/共90页第二十三页，共90页。J.Chem.Res.(s),2001,32Yield:60-72%第23页/共90页第二十四页，共90页。Tetrahedron Lett.1998,39,8491第24页/共90页第二十五页，共90页。Heteroatom Chem.2001,12,539 S SRNRN1 Reaction of Haloarenes with Benzenethiolate,1 Reaction of Haloarenes

5、with Benzenethiolate,Benzeneselenolate,and Benzenetellurolate ions Promoted Benzeneselenolate,and Benzenetellurolate ions Promoted by SmIby SmI2 2第25页/共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。金属钐金属钐/辅助试剂促进辅助试剂促进(cjn)(cjn)的有机反应的有机反应第27页/共90页第二十八页，共90

6、页。Synlett,1999,1065Sm/I2(cat)Sm/I2(cat)体系体系体系体系(t(t x)x)Synth.Commun.,1997,27,1043Tetrahedron Lett.,1997,27,1065第28页/共90页第二十九页，共90页。Tetrahedron,1999,55,10695 Sm/NH4ClSm/NH4Cl体系体系体系体系(t(t x)x)第29页/共90页第三十页，共90页。Sm/HOAcSm/HOAc体系体系体系体系(t(t x)x)Chin.J.Chem.2001,19,914 Only(E)-cinnamates(J=14-18Hz)(Z)-ci

7、nnamates(J=6-12Hz)was not detected第30页/共90页第三十一页，共90页。Yield:61-91%J.Chem.Res.(s),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),1999,214Sm/Cp2TiCl2 Sm/Cp2TiCl2 体系体系体系体系(t(t x)x)第32页/共90页第三十三页，共90页。Sm/TiCl4 Sm/TiCl4 体系体系体系体系(t(t x)x)Yield:52-81%Synth.Comm

8、un.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 Chem.1999,10,203 Sm/HgCl2 Sm/HgCl2 体系体系体系体系(t(t x)x)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 Sm/CrCl3 Sm/CrCl3 体系体系体系体系(t(t x)x)第35页/共90页第三十六页，共90页。Synth.Commun.,1997,27,2749,Ibid,1999,10,899

9、,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.2000,11,195 Sm/BiCl3 Sm/BiCl3 体系体系体系体系(t(t x)x)第37页/共90页第三十八页，共90页。Chin.J.Chem.2000,18,69 Sm/SbCl3 Sm/SbCl3 体系体系体系体系(t(t x)x)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.R

10、es.(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。钐试剂用于合成钐试剂用于合成(hchng)S(hchng)S、SeSe、TeTe杂原子化合物杂原子化合物第40页/共90页第四十一页，共90页。Synth.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.,1998,6,350Synth.Commun.,1996,26,1517Synth.Commun.,1996,26,3277Synth.Commun.

11、,1998,28,2657第42页/共90页第四十三页，共90页。J.Chem.Res.(s),1998,598Z=CN,COOMe第43页/共90页第四十四页，共90页。Synth.Commun.1996,26,1417 Tetrahedron Lett.,1994,15,8833 Synth.Commun.1996,26,3283 第44页/共90页第四十五页，共90页。烯丙基溴化钐在有机合成烯丙基溴化钐在有机合成(yuj hchng)中的应用中的应用第45页/共90页第四十六页，共90页。Allylsamarium bromide induced monoallylation react

12、ionsAllylsamarium bromide induced monoallylation reactionsChin.J.Chem.,1999,1,1第46页/共90页第四十七页，共90页。Synth.Comm.,1997,27,1495The synthesis of Homoallylamines by the addition of organosamarium reagent to nitrilesThe synthesis of Homoallylamines by the addition of organosamarium reagent to nitriles第47页/

13、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 reaction of acyclic amides with allylsamarium bromideTetrahedron Lett.2001,42,8507第50页/共90页第五十一页，共90页

14、。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 and succinimide with allylsamarium bromide第53页/共90页第五十四页，共90页。Samarium Induced Allylation of Lactones A Fa

15、cile 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。钐试剂钐试剂(shj)促进的环化反应促进的环化反应第56页/共90页第五十七页，共90页。Tetrahedron Lett.1997,38,8063 Cyclodimeriaztion of Arylidenecyanoacetate Promoted by SmICyclodimeriaztion of

16、Arylidenecyanoacetate Promoted by SmI2 2第57页/共90页第五十八页，共90页。mechanism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 SmI2J.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。Tetrahedron Lett.1998,39,5257Te

17、trahedron 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。mechanismmechanism第63页/共90页第六十四页，共90页。Water Accelerated Sm/TMS

18、Cl System:Reductive Water Accelerated Sm/TMSCl System:Reductive Dimerization Cyclization of 1,1-dicyanoalkenesDimerization Cyclization of 1,1-dicyanoalkenesTetrahedron 1998,54,11129第64页/共90页第六十五页，共90页。Synth.Commun,2000,30(4),597 Cyclodimerization of,Cyclodimerization of,-unsaturated Ketones Promoted

19、 by-unsaturated Ketones Promoted by SmISmI2 2第65页/共90页第六十六页，共90页。SmISmI2 2 Promoted Intramolecular Ketone-nitrile Reductive Promoted Intramolecular Ketone-nitrile Reductive Coupling ReactionsCoupling Reactions第66页/共90页第六十七页，共90页。Synthesis,2000,(1),91 第67页/共90页第六十八页，共90页。Intramolecular Ketone-ester R

20、eductive Coupling Reactions Promoted by SmI2Tetrahedron Lett.2001,42,5745第68页/共90页第六十九页，共90页。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.Chem.Lett.,2000,11(5),389Synthesis of 3,4-dihydro-(2H)-1,2,4-benzothiadi

21、azine-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。J.Indian Chem.Soc.,2001,78,314SmI2 Promoted Reductive Cyclization of Nitrodisulfide

22、s 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 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-benzoth

23、iazepin-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 Aid 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-benzothiadi

24、azine-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-benzodiazepinesYield:78-85%Chin.J.Chem.2001,19,996 第78页/共90页第七十九页，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-dih

25、ydro-1H-1,5-benzodiazepines第79页/共90页第八十页，共90页。mechanismmechanism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 Access to 2H-1,4-benzoxazine DerivativesJ.Chem.Res(s).2000,385第81页/共90页第八十二页，共90页。Synthesis of Dihydrofurans from Diaryl Ketones and Chalcone

26、s Promoted by SmI2/SmSynthesis 2001,7,1004第82页/共90页第八十三页，共90页。Convenient Preparation of Polysubstituted 3H-pyrroles Promoted by SmI2J.Chem.Soc.Perkin 1 2001,2836mechanismmechanism第83页/共90页第八十四页，共90页。Synthesis of Polysubstituted Cyclopentenamines by SmISynthesis of Polysubstituted Cyclopentenamines b

27、y SmI2 2 Yield:63-79%Yield:63-81%Yield:55-90%第84页/共90页第八十五页，共90页。mechanismmechanism第85页/共90页第八十六页，共90页。Synthesis of Functionalized 2,3-Dihydrofuran by SmISynthesis of Functionalized 2,3-Dihydrofuran by SmI2 2Yield:51-83%mechanism第86页/共90页第八十七页，共90页。Synthesis of Functionalized 2,3-Dihydropyrroles by SmISynthesis of Functionalized 2,3-Dihydropyrroles by SmI2 2第87页/共90页第八十八页，共90页。mechanismmechanism第88页/共90页第八十九页，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页第九十页，共90页。