有机合成方法ppt课件.ppt

有机合成方法有机合成方法蔡春教授,博士生导师南京理工大学化工学院课堂教学内容课堂教学内容1.有机合成的基本概念和实验方法2.官能团的转化3.有机分子设计4.保护基团技术5.现代有机合成化学热点1.有机合成的基本概念和实验方法有机合成的基本概念和实验方法n基本的有机合成反应:游离基反应;取代反应;加成反应;氧化和还原;重排等n有机合成实验的基本规则:实验方案的设计;反应过程的判断和跟踪;产物的定性和定量等n有机合成的主要文献基本的有机合成反应基本的有机合成反应游离基反应:卤化反应(烷烃,芳环侧链等) 分子氧进行的氧化反应 (醇,醛,酮)聚合反应(自由基聚合)游离基的产生游离基的产生CH3CCH3O紫外光CH3COCH32CH3CO60(CH3)4Pb600PbCH3C6H5CO)2O(C6H5COOC6H5CO2H+eHCH3CCH3OHCH3CH3COH饱和碳上的亲核取代反应饱和碳上的亲核取代反应SN1, SN2机理，碳正离子中间体X-CRRRYCXYRRRCXRRR由醇制备卤代烷、卤代烷的水解 形成形成C=C重键的消除反应重键的消除反应卤代烷中脱卤化氢：E1，E2，E1cb机理季铵碱中消除三烷基胺（Hoffmann降解），该类反应要求有-HRCH2NCH2CH2OHCH3CH3RCH2NCH3CH3CH2CH2向活化和非活化向活化和非活化C-C重键的加成反应重键的加成反应烯烃和炔烃的亲电加成：卤素、卤化氢、次卤酸、硫酸等RCHCH2H2SO4RCHCH3OSO3H亲核加成反应 多见于活化双键，如Michael加成 HCCHRONaROHCH2CHORCH2CHCOORROHROCH2CH2COORROCH2CHCOHOR芳香族化合物的亲电和亲核取代反应芳香族化合物的亲电和亲核取代反应亲电取代反应：硝化、亚硝化反应磺化反应卤化反应（金属或路易斯酸催化）F-C烷基化反应由羰基化合物进行的亲电取代： Vilsmeier甲酰化反应 ArHNCHOC6H5CH3POCl3ArCHOHNC6H5CH3亲核取代亲核取代ClNO2OH-OHNO2NRLiNR氧化和脱氢氧化和脱氢 甲基、次甲基的氧化伯醇、仲醇、醛、酮的氧化C-C键的氧化裂解常用的氧化剂常用的氧化剂 应用过氧化物的氧化过氧化氢或过氧化有机酸 RCHCH2CH3CO3HRCHCH2O单过硫酸（Caro酸）：常用于环酮合成内酯 CCOH2SO5COCO含氧的高价无机化合物 HOOHCrO3CH2Cl2OO二氧化硒是一种具有特殊性的氧化剂，它比较专一地氧化羰基的-甲基或亚甲基及C=C双键旁的-亚甲基：CH3CCH3OSeO2CH3CCHOO脱氢脱氢 是加氢反应的逆反应，原则上加氢催化剂亦可用作脱氢催化剂，常用的脱氢催化剂是一些金属的氧化物，如Cr2O3, ZnO, Fe2O3等 CH2CH3CHCH2Fe2O3-K2CO3-Cr2O3540还原和加氢还原和加氢 不饱和键的加氢硝基的还原常用的还原剂：催化氢化：催化剂的选择性可以通过配体来调节 OH2, C6H6(Ph3P)3RhClO化学还原法化学还原法有两种主要形式:其一是电子，对不饱和化合物进行加成，继而质子转移，该方法中金属作为电子的来源，水、醇、酸作为质子的供给体 CH3CCH3ONa/NH3C2H5OHCH3CHCH3OH其二是氢负离子加成，接着以独立的一步发生质子化，应用最广的氢负离子转移试剂是氢化铝锂和硼氢化钠 CH2CHCHCHCHOLiAlH4CH2CHCHCHCH2OH羰基化合物的反应羰基化合物的反应羰基化合物与碱的反应：醛、酮与氨基化合物的反应RCCH2RORNH2RCOHNHRCH2RRCCH2RNR醛、酮与水、醇的反应 RCCH2ROROHH+RCOHORCH2RROHH+RCORORCH2R羰基化合物与C-H酸性化合物的反应HCN对醛、酮的加成RCROHCNRCROHCN羰基化合物的乙炔化RCRORCROHCCHHCCH醇醛缩合反应醇醛缩合反应酸、碱均可以催化该反应RCOCH2RRCOHCH2RCHRCRO羰基化合物与隐碱的反应格氏(Grignard)反应 有机锂试剂与羰基化合物的加成RMgXCOR1R2CR1R2ROMgXH2OH+CRR1R2OHLiCH2COOLICORR1CRR1CH2OHCOHO重排反应重排反应碳正离子引起的重排 CRROHCRROHH2OH+CRRCRROHCRRRCRO卡宾引起的重排如以重氮甲烷和酰氯生成的重氮酮的重排 RCClOCH2N2RCCHN2ORCCHN2ON2RCCHORCHCOH2OROHNH3RCH2COOHRCH2COORRCH2CONH2氮宾引起的重排（Hofmann降解） RCNH2OBr2NaOHRCNOHBrHBrRCNORNCOH2ORNHCOOHCO2RNH2芳香族化合物的重排反应Fries重排联苯胺重排NRNOHXNHRNONHRNONHNHH2NNH2环化反应环化反应电环反应多烯烃化合物的体系的末端可以闭合成环状化合物 heatlight环加成反应Diels-Alder反应CHCOOC2H5CHCOOC2H5COOC2H5COOC2H5卡宾及氮宾对不饱和键的加成反应CCCCCCNCCCCN有机合成实验的基本规则反应的后处理: 挥发性,极性,稳定性反应产物的分离和纯化: 蒸馏,升华,重结晶,水蒸气蒸馏,层析纯度的标准和纯度的检验: 熔点,沸点,旋光度(已知化合物) GC,TLC,HPLC(未知化合物)有机合成的主要数据库常用数据库:nSDOSnACS publicationnSpringernWiley intersciencenTaylor & FrancisnRSC有机合成的重要文献1.Tetrahedron Letters2.Journal of Organic Chemistry3.Chemical Communication4.Chemical Reviews5.Accounts of Chemical Research6.Chemistry Letters7.Journal of American Chemical Society8.Organic Letters9.Synthetic Communication10.Organic Process Research & Development2.官能团的转化烯烃CCCCHOHH2O+CCHOCCH3OheatCCOOCS(RO)3PCCHXX=hal, OSO2RbaseCC(CH3)3SiHICCPd/C/H2: ZLi/NH3: ECOCPPh3乙烯基硅烷氢交换 OAcOAcHSiEt3Et3SiOAcOAcHIOAcOAc三乙基硅烷与炔烃发生选择性加成，经氢交换后可得顺式加成产物-二醇消除羟基 OHOHOOCSCSCl2(RO)3P反应过程利用生成环状中间体而保持构型，继而进行顺式消除，立体定向地生成顺（或反）异构烯烃 炔烃RCCCCHRhalbaseRCCHHhalhalbaseRCCHHhalhalbaseCCNaRhalRCCNNNH2H2NRCONNHTos氧化二酮的双腙制备炔烃 OONH2NH2NNH2NNH2O2CuCl氯化亚铜/吡啶/氧的配合物使二腙进行氧化裂解，失去氮气生成炔烃 ,环氧酮的对甲苯磺酰腙的裂解反应 OOTosNHNH2NNHTosOheatO氧化异佛尔酮卤代烃CCOSO2RX-CCXCCOHHXPX3, SOCl2CX4/PPh3亲核取代亲核取代CCHX(含HF)卤代烃COCXCOCHOOOOBrBr亲电取代(CH3)3SiOCCX2(CH3)3SiOCCXXCCCXCCCXNOOX亲电取代X=Cl, Br, I醇CCOHCCONaBH4, LiAlH4CCOROLiAlH4CCONa, NH3LiAlH4CCBH3, H2O2,NaOH(反马规则)Hg(OAc)2, NaBH4(马氏规则)CCOH OHOsO4(cis diol)N2O, H+(trans diol)H3COHOOKBH4H3COONaOHH2OH3COHOHO酮酸中羟基的选择性还原，产物以内酯形式生成 烯烃的硼氢化反应 CH2OHBH3, THFNaOH, H2O2蒎烯 （）-（）-顺式桃金娘烷醇醚和环氧化合物COCO-CXX-COHCCRROCCRRRCO3HCCRRH2O2OH-COH2CSRR醚用作保护基团CHOOCH3OHPhCH2ClCHOOCH3OCH2PhCH2COOHCOOHOCH3OCH2PhCHCHCOOHH2Pd/COCH3OHCH2CH2COOH二氢阿魏酸锍叶立徳与羰基化合物环氧化 SH3CCH3CH3IH2CSCH3CH2PhPhOPhPhOHH含硫化合物R1S-XRR1SRNa2S2XRNaXRSRRSROOR1XSRRR1X三烷基锍盐（锍叶立 ）ORSROO砜R1XSRRR1OX氧化锍叶立RSO2ClRSO2H (亚磺酸)H一定条件下产生的硫自由基，可以和卤代烷进行反应生成硫醚，产物的收率较高 BrR78.CBuLiSSRRCH2BrSRR98%Tetrahedron Lett., 2002,43:2145胺(伯胺)RNO2HRNH2RCXOX=NH2 Hofmann重排X=N3 Curtius 重排X=OH NH3 Schmidt 重排X=NHOH Lossen 重排RCNHNH3RXCCRRRRNCCH3Hg2+(H. C. Brown酰胺汞化反应)Delepine反应合成伯胺 NNNNNNNNCH2PhClCH2PhClSO2PhCH2NHCH2OSO2H亚磺酸苄氨基甲酯HClKOHPhCH2NH2胺(仲胺)RNH212HC(OR)3H2O, H+RNHRRNH2CR1R2ORNH2RXRNH2CN胺(叔胺和季铵盐)RNH2(CH3)2SO4RNRRRNH2HCHOHCO2H(RNHCH2OH, RN=CH2, RNHCH3)R1XNRRRR1X醛RCHORCH2OHCr2O72-/H2SO4PCC, PDC, MnO2RCClOLiHAl(OtBu)3RCN氢化二异丁基铝（DIBAH）RCH2XX=hal, OTosDMSOLiHAl(OEt)3RCN(CH3)2ORXX=hal1 Mg2 HCO2MgX(Vilsmeier合成芳醛)酮RCR1OCRR1OHHCr2O72-/H2SO4ArHR1CClOlewis acidRCClOR1MgXR1CdR1MgXRCNNO(Meyers醛合成法，N季铵化、水解得醛)氯铬酸吡啶鎓盐 (PCC)OHNa2Cr2O7H2SO4HO85%PCC: NHClCrO3NHClCrO3重铬酸吡啶鎓盐 (PDC)CrO3C6H5NH2O(C6H5NH)2Cr2O72PDCOHPCC/Al2O3O薄荷酮OHPDCCH2Cl2HO香茅醛Kornblum氧化反应 氧化对甲苯磺酸酯合成醛（DMSO，Kornblum氧化反应） OHH3CSO2ClNaOHOSO2PhCH3HODMSONCH3CH3OLiHAl(OtBu)3HOLiAlH4NCH3CH3CNDIBAH酸性水解碱性水解HOCHNHDIBAH: (CH3)2CHCH22AlH, 二异丁基氢化铝醛(酮的衍生物)CHCOCCNXX=R, OH, NHRH2NXCHCORORH(COR)3ROHCCORCCH2Zn/Hg, HClH2NNH2, OH-HNR2CCNR2R2HNR2CCNR2HS(CH2)nSHCCSS(CH2)nHO(CH2)nOHCCOO(CH2)nn=2,3n=2,3烯胺烷基化反应 OCH3ONCH3ONCH3ICH3OCH3NIH2O, H+CH3OCH3O选择性差羧酸RCO2HRCHOCrO3KMnO4RCH2OHCrO3KMnO4Nickel peroxideArCCH3OTl(NO3)2吗啉RCCH3OKClOKMnO4(only for cyclic ketones)RCH3(R=phenyl)KMnO4Cl2, hr/NaOH/HClH2SO4RCNRM (M=Li, MgBr)CO2硝酸铊（III）使芳酮起氧化重排反应 CCH3OCCH2OHOCCH2BrOTl(NO3)3/K10CH2COHOCCH2CH3OCHCH3COHOCCH2CH2CH3OCHCOHOC2H5对其它芳基酮的氧化主要产物是2-取代苯乙酸 次氯酸盐氧化甲基酮 CH3CH3CCHCCH3OKClOCH3CH3CCHCOHO(千里光酸)次氯酸盐氧化甲基酮，生成少一个碳原子的羧酸 羧酸衍生物RCOHOSOCl2PCl5RCClORCOCROOROHH+RCOROROHbaseHNR2, H2ORCNRROHNR2baseHNR2i5-7-gfedcbaedcbaihgfedcbahgfedcbahgfedcba6-4-3-1-2-ihgfedcbaC=C-C(O)-CH3CH-CHCH-CXF Fu un nc ct ti io on na al l G Gr ro ou up p I In nt te er rc co on nv ve er rs si io on nC=CC CC=CC CRCH2-SO2PhRC CHC CC-NH2; C-NO2C-OHC(OR)2; C(SR)2C=C-OR; C=C-SRC CC NC=N-OH, C=N-HC=SC=OC=OC-C(O)ZC=CC=OC-OHC-XC-NC-HC-NC=OC-OHC-OC(O)RC-XC-OCH2ORC-NH2C-ORC-HC-OHC=CC-HC(O)ORC-(OR)2C-OHC-ORC-CHOC-CO2HC-CNC=CC=OC-SC-XC-OHC-HC=CjC(O)XhC NjkC-HC-Br8-C-XiC-OHC-OHC(O)ZdcbaedcbafC-NH2C-HjCX-CYCCXC=OhgfiC CHRCH(CO2H)-CH3-C(O)-CH3OOOXCRR=CHXjC OC-NH2C-CN9-C-CH3C-XaeC=O1-adry pyridine: from CaH2 and distilled(an ester)triflatemesylatetosylateSOOORCH2CF3SOOORCH2CH3thiocarbonatedry PyCH3CH3CH3OH(2). for 3 alcohol:LiAlH4(1). for 1, 2 alcohol: C-HC-OH1-ihgfedcbaC-CHOC-CO2HC-CNC=CC=OC-SC-NH2C-XC-OHC-HO CSO PhSnBu3CH3CH3CH3Hn-Bu3SnHCSOPhClO CSO PhRCH2-HCH3SOOORCH2CH3SOOClRCH2OHsteric OKpurification textbook $ 30 / Kgtoluenesulfonyl chloride (s)methanesulfonyy chloride (l) $ 30 / KgjC(O)XPh2SiHCl / InCl3PhPhHPhOHPhJOC, 2001, 66, 7741.ii. Ph2SiHCl / InCl3i. p-TsCl / LiAlH4i. ClC(S)OPh / n-Bu3SnHPhPhOCl2InCl SiPh2Hvia:via:a unique Lewis acid catalyst, acceleratedeoxgyenationInCl3indium trichlorideii. Et3SiH / Lewis acid J. Org. Chem. 2000, 65, 6179JOC, 2000, 65, 6179.CHCl2rt, 3 hr1-bBu3SnH: (l), easy to removePh3SnH: (s), hard to removeMe3SnH: too volatile, toxic(AIBN)NNCNCN- N2CNazobisisobutyronitrilen-BuSnHn-BuSnBrRn-BuSnBrRHRunstable in acid, form H2 gas; stable in weak baseNaBH3CN: stable at pH 5-6hygroscopic, dried self, suggest: buy small amount each time(Grignard reagent)H2OMg / Et2OJOC, 1969, 34, 3923.HBrNa / NH3; Li / NH3; Na / EtOHZn; Fe; Sn; Mg(3). metal reduction(2). hydride reduction(1). free radical reduction JACS, 1972, 94, 8905.C-HC-XAIBNn-Bu3SnHHBrradical initiatorNaBH4 / InCl3 / CH3CNradical reagentn-Bu3SnH / AlBNJACS, 2002, 124, 906.iiii NaBH3CNi LiAlH4iiiii NaBH4iiTHL, 1969, 3095.JOC, 1976, 41, 3064.iv LiBHEt3 (super hydride)n-BuSnHn-BuSnmechanism uncertain, probably radicalburn filter paper if dryRaney Nickel: Ni - Al alloy, suspensiontosylimidetosylamideJCS Perkin Trans I, 1973, 654.(3). LiAlH4 / CuCl2NaBH4 / NiCl2NaBHEt3 / FeCl2 (or CoCl2, VCl3)(2). Li / NH3(1). Raney NiNSO2ArSO2ArRCH2RCH2NSO2Ar- BuHRCH2NHSO2ArBuLiLiAlH4RCH2-HCH3SOOClRCH2NH2BuLi1-d1-cC-HC-SLiAlH4C-HC-NH2RCH2-HRCH2NH2Hinsbergs testradical mechanismweaker C-N bondChemistry:R-SHR-S-RR2SOR2SO2R-SS-Rremove: Hg+; Ni(1).(2).Ar-HNaNO2HClH3PO2Ar-NH2RCH2NH2RCH2NMe3R=CH2R-CH3(4).X-RCH2NMe3OH-Ag2OJOC, 1985, 50, 427.p-TsClNaHNaHp-TsClNH2Clvia:NNH2SO2ArArNaHNNHArNNArAr-H- ArSO2H(3).Ar-NH2Ar-Hp-TsClJOC, 2001, 66, 8293.ArSO2ClRaney NiNHNSMeO2CCH2PhEtO2CONHNHMeO2CCH2PhEtO2Cfor acyclic, may C=C side productbasicneutralacidicHHH-N N TsCH2Cl2C=OC-H1-e(1). Clemmensen reduction: Zn-Hg / HCl(2). thioketal: (3). Wolff-Kishner reduction:(5). Tosylhydrazone reduction (Shapiro reaction): (modified Wolff-Kishner reduction):)(6). enol derivatives: SHSH/ BF3, CH2Cl2 / RaNiN2H4, OH-, heatTsNHNH2 / REDlimit: for -H compd.HHRa(Ni)BF3,SSHHSSHHOthioketal: inert to LAH; react with RaNi; smell terrible and stay long; discard shosesthioketalmajor side-product: drawback of the reactionNN- N2OH-HNNHN NHOH-NNH2N2H4OHHNCHCOCF3SOOOSOCF3OCCOTfH2PtO2CCHHHTf2O / N/ H2 / PtO2LAH, NaBH4: 2 group compete at Stanford U.B2H6: very flamable, fire if shoot out from syringeOOB Hbest suitable for aryl ketone (ArCOR); not good for conjugate ketone preparation: HgCl2 into ZnRED choice: MeLi; NaBH3CN (good)PtO2 + H2 = PtOHOC6H13similar: Sn / HCl(4). Pd-C / HCO2NH4: mild, efficientPhPhOPhPhSynthesis, 2001, 16, 2370.HCO2NH4Pd-C(7). Et3SiH / CF3COOHPhONO2PhNO2JOC, 1973, 38, 2675.CF3COOHEt3SiHHOOHHHPtO2H2HOOH$ 50 / 25 gJOC, 1993, 58, 4979.syn-additionprepare isotopeCH3CO2DHDC=CC-C-H1-f(1). H2 / cat(2). HN=NH (diimide)(3). B2H6 / RCO2H, heatWilkinsons catalyst: regioselective, prefer isolated double bondsoluble in org solvent, 9 Ph groupstereoselcetive: same side as OH (due to H bond)catalyst: Pd-CPtO2Rh-C; Rh-Al2O3; RhCl(PPh3)3NiOORhCl(PPh3)3N2H2: unstable; generated in situ from DEAD (diethyl azodicarboxylate) or from: N2H4 + H2O2; N2H4 + Cu(II) + O2; NH2OH + NH2OSO3via: HB RRNNCO2EtEtO2CNNCO2HHO2COH- 2 CO2NNOOHOOHNNHH- N2CCRRRRCCRRRRHHJCS, PT1, 1986, 546.OOCO2MeOOCO2MeRhCl(PPh3)312 hrJACS, 1979, 101, 7020.NRNRH2 , PtO2TFA , 60 R = NHAc , NH2JOC, 2002, 67, 7890.in acetic conditionbenzene(4). n-Bu2SnI / MgBr2-Et2O / H3O+OEtOH3O+OEtOMgBr2-Et2On-Bu2SnIJOC, 2001, 66, 8690.OSnHOEtIRROOEtSnIRHRvia:not radical mech.pyridinium betainesolventNPhPhPhRRHNPhPhPhRRCO2- CO2b.p. 230 Chighly toxic, cancer suspected agent?= HMPT: hexamethylphosphoric triamide (Me2N)3P=Otoxic?characteristcs: IR, CMRwhich is + ?CCRNnot quite same: not for H-e-CO2HCO2H(3). organic electrochemistry-CO2(1). particular structure: C-H1-g(1). K / Al2O3 K / HMPA(2). Na / NH31-h(2). normal structure: SOCl2 / PhSeH / n-Bu3SnHC CNJOC, 1980, 45, 3227CN: X (pseudo halogen), form KCN, NaCN with IA elementsHMPA: hexamethylphosphoramide (Me2N)3P=Oyes for white mouse, uncertain for humanmodified to: NNOC CO2HC-HCOSePhRCH2RCH2HCOOHRCH2COClRCH2PhSeHn-Bu3SnHSOCl2(radical mechanism?)other Cl sources: PCl5; (COCl)2oxalyl chlorideorganoselenium chemistryOHORO1-iCHOC-H(1). RhCl(PPh3)3 (Wilkinsons cat)(2). Rh(DPPD)2+ Cl-oxidative additionrearrangementreductive eliminationRhPPh3PPh3CClO+RHRhPPh3PPh3CROClHRhPPh3PPh3ClHRCORCOHRhPPh3PPh3Cl- PPh3ClRhPPh3PPh3PPh3DPPD = Ph2P-CH2CH2-PPh21-jC(O)X-CH3RClORCH3HSiEt3 / B(C6F5)3JOC, 2001, 66, 1672.OOOOHAlCl3LiAlH4activator / hydride sourceHOCH3HClOCH3OCH3OCH3RCH2 OROORRORORRCH2 OCH2CH2OH(3). AlCl3 / LiAlH4(2). HCl / NaBH3(CN)(1). h / HSiCl3RC-(OR)2RC-OR2-bSiPhPhClSiCH3CH3ClCH3SiCH3CH3ClNNH/ TBDMS-ClTBDPS-ClEt3N / TMS-Clacid: H2SO4H3PO4BF3-Et2ORC-OCH2CH=CH2RC-OCPh3 = RC-OTrRC-OtBuRC-OCH3RC-OSiR3RC-OCH2Ph = RC-OBZl = RC-OBni. Willianson synthesis OK: Si - Cl bond longii. stability of silyl in acid/base: RC-O-TBDPS RC-O-TBDMS RC-O-TBSiii. abbrev.: TBDMS = tert-butyl-dimethylsilyl = TBS = Silyl group:(RO-Tr)Trityl group: (tirphenylmethyl)i. SN1 reactionii. abbreviation: triphenylmethyl = trityl = -CPh3 = -Triii. advantage: high MW, easy to handle (small amount become large amount)baseBrWillianson synthesis (base, SN2) not work: elimination side-product with baset-Butyl group:i. abbreviation: benzyl = PhCH2 = Bzl = Bnii. deprotecting: H2 / Pd-CPhCH2-ClPhCH2-Br: reactivity goodPhCH2-I: reactivity better than PhCH2Br, generated in situ, PhCH2Br + NaIPhCH2-X: Benzyl- group:i. Williamson ether synthesis, SN2 typeii. not a good protecting group, too stable to convert back to alcoholMe group:CH3-X: CH3I; CH3OSO2R; (CH3)3O+ BF4-, (CH3)2SO4base: NaH, n-BuLi, Ag2O(4). t-Bu: acid cat / (3). allyl: base / Br(6). silyl: Et3N / R3SiCl(5). trityl: py / Ph3C-Br(2). PhCH2-: base / PhCH2-Xapplication: for protecting groupedcba2-RC=CRC-HRC(O)ORRC-(OR)2RC-OHRC-ORRC-OHRC-OR(1). Me: base / CH3-X2-a(7). acetal / ketal: (see 3e)fRC-CNgenerate H2, or butane gasJOC, 1988, 53, 2985.trimethyloxonium tetrafluoroborateJCS, 1930, 2166.(8). ArF / CsFROHFNO2RONO2aromatic substitution reactionusually contain NO2, F as leaving groupCsFsee mech-13hvI2 / Pb(OAc)4 OOHOIHOHOIlimit: for 56 ring neighboring OH group(1). I2 / Pb(OAc)4 / hvradical mechanism: SiCl3t-BuORaNi with C=SJOC, 1983, 48, 1127.JOC, 1974, 39, 2470.RaNiLawesson reagentSOOOO P4S10tBu-OO-tBuHClOOOR COOR2-cRC-OR2-dRC-ORRC-H(1). hv / HSiCl3(2). HCl / tBu-OO-tBu(3). Lawesson reagent / RaNi(4). BF3 / NaBH4PSPSSSOCH3CH3OOOOOArArOOArArBF3NaBH4Lawesson reagent(2). Organoelectro Chemistry: e- / Pt, R4NOTsNOHPhNOPhe/ PtR4NOTs(79 %)NOHPhRRMgBrAngew Chem Int Eng., 1964, 8, 525.limit for: lactoneHNNHNH2OHHHNNHNH2OOCH3 NCS(3). NCS / MeOHMeOHJOC, 2002, 67, 4498.limit: for allylic alcoholC-C-OR2-eC CCCONaBH4OEtCO2EtOHCO2EtHHOHHOHOOi. Hg(OCOCF3)2, ROH / NaBH4i. peracidii. via halohydrin: HOBr, H2O / K2CO3iii. Sharpless asymmetric epoxidation: t-BuOOH, Ti(OiPr)4 / (+)-diethyl tartrateHg(O COCF3)2OOmCPBAH2OHOBrBrBrOHtrans-diaxial attack!Olimit for allyl alcohol, high e.e.Sharplessstereoselectiveracemic productsHg O+COCF3racemic productsHOBr generation: NBS + H2O + DMSOOOconversion: HOAcOHOAcOSO2MeOAcEtOHC=C-ORC=C-ORC-C-ORC CC CC CCCO2-e.12-e.22-e.3ii. HCHOPrins RxnOSO2MeOHOOOHOHOHHCHO (aq)OOvia:H2OHCHOSynthesis, 1980, 871.CO3HCO3HClCF3CO3HCO3HCO2Hgood resultperoxybenzoic acidMCPBA(m-chloroperoxybenzoic acid)stable solid, 85 % (contain MCBA) for safetyperacid:iv. t-BuOOH, Mo(CO)6v. KHSO5vi. H2O2, t-BuOH, MnSO4 / NaHCO3, pH 8JACS, 2001, 123, 2933.HO2CHO2COnew, cheap, simple, green chemistrypotassium hydrogen preoxideconvenient, inexpensive, powerful.JOC, 1980, 45, 4758.JOC, 1982, 47, 2670.OOHOOBr2via:Br2 / ROHOOBrHHeterocyclic Chem, 1990, 27, 583.C-C-OR2-fC NCROH / HClEtCNEtCOEtOEtOEtEtOHHClJACS, 1942, 64, 1825.(+)-diethyl tartratechiral sourceJOC, 2001, 66, 521.C-OHC-HC-ORC-NH2C-X3-abcd3-aC-OHC-HOH(1). PhI(OAc)-O2-Mn(TPP)(2). organic electrochemistryPhI(OAc)-O2-Mn(TPP)JACS, 1983, 105, 3515.JACS, 1983, 105, 2920.NO2NH2OHe-H2O(3). X2 / hv / OH-indirectHOHOHOOHHOH3-a.13-a.23-a.3HROSeOROHSeHOORSeOHROHSe(OH)2H2ORHROHSeO2JACS, 1972, 94, 7154.SeO2for allyl H:(1) Me3SiCl / MPCBA/H3O+(2). O2, LDA, (EtO)3PROCO2RROCO2ROHOOROROOPOEtOEtvia:JACS, 1975, 97, 6909.PhOPhOSiMe3OPhOSiMe3PhOSiMe3OHOHPhOOH1. Me3SiClMCPBAJOC, 1975, 40, 3427.H3OO2, LDA,(EtO)3PPhOPhOOH2. MCPBAMe3SiClihgfeC=OC-OHC-OC(O)RC-OCH2ORC=CjC O(1). Me: application: deprotecting(2). PhCH2- (5). trityl: (6). silyl: (3). allyl: (4). t-Bu: RC-OCH2Ph = RC-OBZl = RC-OBnRC-OSiR3RC-OCH3RC-OtBuRC-OCPh3 = RC-OTrRC-OCH2CH=CH2C-OHC-ORNi. TMSIii. BF3-Et2O / R-SH (or HS-CH2CH2-SH)iii. BBr3 / CH2Cl2, 0-10 C/ LiI, heatvi. RCH2-OHRCH2-O-SiMe3Me3Si-IRCH2OCH3SiMe3- CH3IRCH2-O-CH3I- I-RCH2-O-CH3RCH2OCH3BF3BF3