1、會計學1有機合成有機合成(yuj hchng)中的保護基中的保護基第一頁，共41頁。碳數 烷烴名稱 英文名稱脂肪烴類化合物的命名烯炔烷基1234567891011121314151617181920methaneethanepropanebutanepentanehexaneheptaneoctanenonanedecaneundecanedodecanetridecanetetradecanepentadecanehexadecaneheptadecaneoctadecanenonadecaneeicosane甲烷乙烷丙烷丁烷戊烷己烷庚烷辛烷壬烷癸烷十一烷十二烷十三烷十四烷十五烷十六烷十七烷

2、十八烷十九烷二十烷-ethylenepropenebutenepentenehexenehepteneoctenenonenedeceneundecenedodecenetridecenetetradecenepentadecenehexadeceneheptadeceneoctadecenenonadeceneeicosene-acetylenepropynebutynepentynehexyneheptyneoctynenonynedecyneundecynedodecynetridecynetetradecynepentadecynehexadecyneheptadecyneoctade

3、cynenonadecyneeicosynemethylethylpropylbutylpentylhexylheptyloctylnonyldecylundecyldodecyltridecyltetradecylpentadecylhexadecylheptadecyloctadecylnonadecyleicosyl烯基炔基-vinylpropenylbutenylpentenylhexenylheptenyloctenylnonenyldecenylundecenyldodecenyltridecenyltetradecenylpentadecenylhexadecenylheptad

4、ecenyloctadecenylnonadecenyleicosenyl-acetylenylpropynylbutynylpentynylhexynylheptynyloctynylnonynyldecynylundecynyldodecynyltridecynyltetradecynylpentadecynylhexadecynylheptadecynyloctadecynylnonadecynyleicosynyl第1頁/共41頁第二頁，共41頁。碳數烷烴名稱英文名稱脂肪烴類化合物的命名-21234567891011121314151617181920methaneethaneprop

5、anebutanepentanehexaneheptaneoctanenonanedecaneundecanedodecanetridecanetetradecanepentadecanehexadecaneheptadecaneoctadecanenonadecaneeicosane甲烷乙烷丙烷丁烷戊烷己烷庚烷辛烷壬烷癸烷十一烷十二烷十三烷十四烷十五烷十六烷十七烷十八烷十九烷二十烷醇-1醛methanolethanolpropanolbutanolpentanolheptanoloctanolnonanoldecanolundecanoldodecanoltridecanoltetradec

6、anolpentadecanolhexadecanolheptadecanoloctadecanolnonadecanoleicosanolmethyl alcoholethyl alcoholpropy alcoholbutyl alcoholpentyl alcoholhexyl alcoholheptyl alcoholoctyl alcoholnonyl alcoholdecyl alcoholundecyl alcoholdodecyl alcoholtridecyl alcoholtetradecyl alcoholpentadecyl alcoholhexadecyl alcoh

7、olheptadecyl alcoholoctadecyl alcoholnonadecyl alcoholeicosyl alcoholformaldehydeethanalpropanalbutanalpentanalheptanaloctanalnonanaldecanalundecanaldodecanaltridecanaltetradecanalpentadecanalhexadecanalheptadecanaloctadecanalnonadecanaleicosanal醇-2酮-acetonebutanonepentanoneheptanoneoctanonenonanone

8、decanoneundecanonedodecanonetridecanonetetradecanonepentadecanonehexadecanoneheptadecanoneoctadecanonenonadecanoneeicosanone第2頁/共41頁第三頁，共41頁。碳 數烷 烴 名 稱英 文 名 稱脂 肪 烴 類 化 合 物 的 命 名 -31234567891011121314151617181920methaneethanepropanebutanepentanehexaneheptaneoctanenonanedecaneundecanedodecanetridecane

9、tetradecanepentadecanehexadecaneheptadecaneoctadecanenonadecaneeicosane甲烷乙烷丙烷丁烷戊烷己烷庚烷辛烷壬烷癸烷十一烷十二烷十三烷十四烷十五烷十六烷十七烷十八烷十九烷二十烷formic acidacetic acidpropionic acidbutyric acidvaleric acidcaprylic acidenanthic acidcaprylic acidpelargonic acidcapric acidundecanoic acidlauric acidtridecanoic acidmyristic aci

10、dpentadecanoic acidpalmitic acidmargaricic acidstearic acidnonadecanoic acidarachidic acid脂 肪 酸 -1hexanecarboxylic acidheptanecarboxylic acidoctanecarboxylic acidnonanecarboxylic aciddecanecarboxylic acidundecanecarboxylic aciddodecanecarboxylic acidtridecanecarboxylic acidtetradecanecarboxylic acid

11、pentadecanecarboxylic acidhexadecanecarboxylic acidheptadecanecarboxylic acidoctadecanecarboxylic acidnonadecanecarboxylic acid脂 肪 酸 -2第3頁/共41頁第四頁，共41頁。BH9-BBN9-borabicyclo3,3,1nonanePPBINAP2,2-bis(diphenylphosphanyl)-1,1-binaphthylCODcyclooctadieneCODcyclooctadieneCpcyclopentadieneOSO3HCSAcamphorsu

12、lfonic acidCe(NH4)2(NO3)6CANcerium(IV) ammonium nitrateDABCO1,4-diazabicyclo2,2,2octaneNN第4頁/共41頁第五頁，共41頁。NSF3DAST(diethylamino)sufur trifluorideDBU1,8-diazabicyclo5,4,0undec-7-eneNNDCCdicyclohexylcarbodiimideNCNOOClClNCNCDDQ2,3-dichloro-5,6-dicyano-1,4-benzoquinoneNNOC2H5OOC2H5ODEADdiethyl azodicar

13、boxylateDHP3,4-dihydro-2H-pyranONISN-iodosuccinimideNOOINNOOOOD DI IA A D Dd di i i i s so op pr ro op py yl l a az zo od di i c ca ar rb bo ox xy yl l a at te eDBN1,5-diazabicyclo4,3,0non-5-eneNN第5頁/共41頁第六頁，共41頁。NBSN-bromosuccinimideNOOBrNMO4-methylmorphine-N-oxideONONHClCrO3PCCpyridinium chlorochr

14、omateNHCr2O7PDCpyridinium dichromate22NHO3SPPTspyridinium p-toluenesulfonatePpyr4-pyrrolidinopyridineNNSO3HPTSp-toluenesulfonic acidNPypyridineTBAFtetrabutylammonium florideNF第6頁/共41頁第七頁，共41頁。TBDPSCltert-butyldiphenylsilyl chlorideSiClTBSCltert-butyldimethylsilyl chlorideSiCH3CH3ClSiCH3CH3OSOOCF3TBS

15、OTftert-butyldimethylsilyl triflateTESCltriethylsilyl chlorideSiClDIBALHdiisobutylaluminium hydrideAlHDMAP4-N,N-dimethylaminopyridineNNDME1,2-dimethoxyethaneOODMFN,N-dimethylformamideHNODMPUN,N-dimethylpropyleneurea1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinoneNNO第7頁/共41頁第八頁，共41頁。HMDS1,1,1,3,3,3

16、-hexamethyldisilazaneSiHNSiHMPAhexamethylphosphoramideNPNONHOBT1-hydroxybenzotriazoleNNNOHImimidazol-1-ylNNLDAlithium diisopropylamideNLiNCSN-chlorosuccinimideNOOClTFAtrifluoroacetic acidOOHFFFmCPBAm-chloroperoxybenzoic acidClOOOHDMSOdimethylsulfoxideSO第8頁/共41頁第九頁，共41頁。TESOTftriethylsilyl triflateSi

17、SOOFFFOF3COOOF3CTFAAtrifluoroacetic anhydrideTfOH triflic acidtrifluoromethylsulfonic acidSOOFFFOHTHFtetrahydrofuranOTIPSCltriisopropylsilyl chlorideSiClTIPSOTftriisopropylsilyl triflateSiOSOOFFFTMEDAN,N,N,N-tetramethylethyenediamineNNTMSBrtrimethylsilyl bromideSiBrTMSCltrimethylsilyl chlorideSiCl第9

18、頁/共41頁第十頁，共41頁。TMSItrimethylsilyl iodideSiITMSOTftrimethylsilyl triflateSiOSOOFFFNRuO4TPAPtetra-n-propylammonium perruthenateTsp-toluenesulfonylSOOTrtrityltriphenylmethylPhPhPhBnbenzylBOMbenzyloxymethylOBzbenzoylOCbzbenzyloxycarbonylOOBoctert-butoxycarbonylOOFmoc9-fluorenylmethoxycarbonylOOTroc2,2,2

19、-trichloroethoxycarbonylOOClClCl第10頁/共41頁第十一頁，共41頁。M M O O M Mm m e et th ho ox xy ym m e et th hy yl lOI Im m i id di im m i i d da az zo ol l i in ne eNHNC C p p* *C C p p- -s st ta ar rAbbreviation 8(Boc)2Otert-butoxycarbonyl anhydrideOOOOO第11頁/共41頁第十二頁，共41頁。第12頁/共41頁第十三頁，共41頁。OHOHHOPivCl (1eq)Py

20、-CH2Cl20-25 oCOHHOOO第13頁/共41頁第十四頁，共41頁。OTBDMSTBDMSOOOOTBDMSTBDMSOOHDIBAL(2.5eq)CH2Cl2, -78 oC95%Nicolaou, K. C.; Webber, S. E. Synthesis, 1986, 453第14頁/共41頁第十五頁，共41頁。OOOBnOAcHNOBnOBnOBnOClAcOOBnOOOOBnOAcHNOBnOBnOBnHOAcOOBnNH2NH2 (15eq)HOAc-HOMert, 12 h74%Cook, A. F.; Maichuk, D. T. J. Org. Chem., 19

21、70, 35, 1940.第15頁/共41頁第十六頁，共41頁。OAcOOORAcOROOROOOOOOPhH2NHNSHSOAcOOOHAcOHOOHOOOOOOPhDioxane, i-Pr2NEtSmith, A.B.; Hale, K. J.; Vaccaro, H. A.; Rivero, R. A. J. Am. Chem. Soc, 1991, 113, 2112.R = ClCH2CO40%第16頁/共41頁第十七頁，共41頁。第17頁/共41頁第十八頁，共41頁。OOOOTBSCOOBu-tCO2MeOHOHMe3SiCl-ImOOOOTBSCOOBu-tCO2MeOTMSO

22、H100 oC, 90 min.100%Kerwin, S. M.; Paul, A. G.; Heathcock, C. H. J. Org. Chem., 1987, 52, 1686第18頁/共41頁第十九頁，共41頁。OHOHOTES OHTESOTf (1.1eq)Py, MeCN, -50 oC, 10 min.79%Heathcook, C. H.; Young, S. D.; Hagen, J. P.; Pilli, R.; Badertscher, U. J. Org. Chem., 1985, 50, 2095第19頁/共41頁第二十頁，共41頁。OBMPOOOHOBzTB

23、DMSOTfOBMPOOOTBSOBzHikota, M.; Tone, H., Horita, K.; Yonemitsu, O. J. Org. Chem., 1990, 55, 7.2,6-di-tert-buylepyridineCH2Cl2, rt, 24 h第20頁/共41頁第二十一頁，共41頁。BnOOHOHOHBnOOTBDPSOHOHTBDPSCl(1.2eq)imidazole(1.2eq)DMF, rt,80%Nicolaou, K. C.; Pavia, M. R.; Seitz, S. P. J. Am. Chem. Soc., 1981, 103, 1224.第21

24、頁/共41頁第二十二頁，共41頁。OHCO2MeOTIPSCO2MeTIPSCl(1 eq)imidazole(2.5 eq)DMF, rt, 48 hBennett, F.; Knight, D. W.; Fenton, G. J. Chem. Soc. Perkin. Trans. I , 1991, 1543.87%第22頁/共41頁第二十三頁，共41頁。OHOTBDPSOMeOHOTBSOHOTBDPSOMeOHOHHOAc-THF-H2O3 : 1 : 1Marshell, J. A.; Sedrani, R. J. Org. Chem., 1991, 56, 5496.87%第23

25、頁/共41頁第二十四頁，共41頁。OOTBSOOOOTBSHOPivHF-CH3CNOOTBSOOOOHHOPivDanishefsky, S. J.; Armistead, D. M.; Wincott, F. E.; Selnick, H. G; Hungate, R. J. Am. Chem. Soc., 1989, 111, 2967.-25 oC85%第24頁/共41頁第二十五頁，共41頁。CO2MeOTBDMSOON3OOTBDMSOTBAFCO2MeOTBDMSOON3OOHONakata, T.; Fukui, M.; Oishi, T. Tetrahedron Lett.,

26、1988, 29, 2219.90%THF, rt第25頁/共41頁第二十六頁，共41頁。TBSOOHTBSOOTBSHOOTBSCollington, E. W.; Finch, H. Smith, I. J. Tetrahedron Lett., 1985, 26, 681.TBAF (1 eq)THF, 0 oCHF (2 eq)MeCN, 50 oC92%83%第26頁/共41頁第二十七頁，共41頁。第27頁/共41頁第二十八頁，共41頁。NOOOOTIPSOHOOTIPSOOTBSOOOOHNOOOOHOHOOHOHOHOOOOHHF / MeCNFK-506, 73%Nakatsu

27、ka, M.; Ragan, J. A.; Sammakia, T.; Smith, D. B.; Uehling, D. E.; Schreiber, S. L.J. Am. Chem. Soc., 1990, 112, 5583.第28頁/共41頁第二十九頁，共41頁。第29頁/共41頁第三十頁，共41頁。第30頁/共41頁第三十一頁，共41頁。OOHHHHO(CH2)3OHOOOHHp-TsOH91%Okawara, H.; Nakai, H.; Ohno, M. Tetrahedron lett., 1982, 23, 1087.第31頁/共41頁第三十二頁，共41頁。OCO2MeOO

28、HOCH2CH2OHTMSCl, rt, 16 hCO2MeOOOO+ (TMS)2OChan, T. H.; Schwerdtfeger, A. E. J. Org. Chem., 1991, 56, 3294.Crimmins, M. T.; Deloach, J. A. J. Am. Chem. Soc., 1990, 112, 1607.HOOHHO(CH2)2OHp-TsOH81%HOHOO第32頁/共41頁第三十三頁，共41頁。HOOHOHOHOHNH2OHOOMeOHOHOHNH2OTMSCl (2 eq.)MeOH, rt, 20 h76%Gerspacher, M.; Rap

29、oport, H. J. Org. Chem., 1991, 56, 3700HOCO2MeCO2MeHOCO2HCO2MeKOH (0.95 eq.)MeOH / H2O95%Honda, M.; Hirata, K.; Sueoka, H.; Katsuki, T.; Yamaguchi, M. Tetrahedron Lett., 1991, 22, 2679.第33頁/共41頁第三十四頁，共41頁。第34頁/共41頁第三十五頁，共41頁。BnO2CNH2OHOBnO2CNH2OO, H2SO4dioxane82%Valerio, R. M.; Alewood, P. F.; Johns, R. B. Synthesis, 1988, 786.NHNOOCO2MeHOAc-i-PrOH-H2ONHNOOHCO2Me100%Gmeiner, P.; Feldman, P. L.; Chu-Moyer, M. Y.; Rapoport, H. J. Org. Chem., 1990, 55, 3068.4:4:1100 oC, 15 h第35頁/共41頁第三十六頁，共41頁。NH2CO2HBoc2O, NaOHHNCO2HOO78-87%Pope, B. M.; Yamamoto, Y.