最新有机化学常见官能团的反应总结.docx

1、最新有机化学常见官能团的反应总结Functional Group InterconversionC-H1- ab cdC-OH C-XC-NH 2C-SC-OR2-ab cC-OHC-(OR) 2C(O)ORC-OH3-ab cdC-H C-OR C-XC-NH 2C-N4-abc dC-HC-NC-X C-OHC=O5-ab c deC=O C=SC=N-OH, C=N-H C CC NeC=OfC=CgC-CNdC-HeC=CfC-CNeC-OCH 2ORfC-OC(O)RgC-OH C=OeC=OfC=CgC-C(O)Zf C=C-OR; C=C-SR g C(OR) 2; C(SR)

2、2 h C-OHhC-CO 2HiC-CHOhi C OhC NiC-NH 2; C-NO 2jC(O)Xj C=Cj C-BrC C C=CC-XC-CH 3kC-H6-a b cdRC CHRCH 2-SO2Ph C CC=C7-ab cCH-CX CH-CHCX-CYX8-ab cdC-OH C-NH 2 C=OC(O)Z9-aC-Xe RCH(CO 2H)-CH 3d C CeC-Hf-C(O)-CH 3gO Oh X Oe-C(O)-CH 3fC=OgC ChC CHiCRR=CHXiC=CjC-OHC-H1-aC-OHe C=Oi C-CHObC-XcC-NH 2dC-SfC=Cg

3、C-CNhC-CO 2Hj C(O)X1-aC-OHC-HJ. Org. Chem. 2000, 65, 6179O RCH 2 O SO OCH3tosylatetoluenesulfonyl chloride (s) $ 30 / Kg(1).for 1, 2 alcohol:OCH3 S ClLiAlHRCH2 O S CH 3O Omesylatemethanesulfonyy chloride (l) $ 30 / Kgi.p-TsCl / LiAlH 4RCH2OHOdry Py4RCH 2-HRCH2 OPh PhS CF 3Otriflatepurification textb

4、ookdry pyridine: from CaH 2 and distilledii.Ph 2SiHCl / InCl 3Ph PhPh2SiHCl / InCl 3 Ph PhCHCl 2via: HOindium trichlorideOH rt, 3 hr H JOC, 2001, 66, 7741.Cl 2InClSiPh2InCl 3a unique Lewis acid catalyst, acceleratedeoxgyenation(2).for 3 alcohol:i.ClC(S)OPh / n-Bu 3SnHCH 3CH 3OHSCl CO Phn-Bu 3SnHCH 3

5、CH 3Hvia:SO C O PhSnBu 3SO C O PhCH 3CH 3thiocarbonateii.Et 3SiH / Lewis acidJOC, 2000, 65, 6179.(an ester)steric OKC-XC-HBr n-Bu 3SnHHi n-Bu3SnH / AlBN(1). free radical reductionAIBNii NaBH 4 / InCl 3 / CH 3CNBu 3SnH: (l), easy to remove Ph3SnH: (s), hard to removeMe 3SnH: too volatile, toxicJACS,

6、2002 , 124, 906.radical reagent(2). hydride reductioniLiAlH 4iiNaBH 4JACS, 1972, 94, 8905.JOC, 1969, 34, 3923.THL, 1969, 3095.iii NaBH 3CNNaBH 3CN: stable at pH 5-6hygroscopic, dried self, suggest: buy small amount each timeunstable in acid, form H 2 gas; stable in weak baseiv LiBHEt 3 (super hydrid

7、e)JOC, 1976, 41, 3064.BrH(3). metal reductioniiiNa / NH 3; Li / NH 3; Na / EtOHZn; Fe; Sn; MgMg / Et O2H O2(Grignard reagent)Brn-BuSnHRHn-BuSnHNNn-BuSnRRCNCN- N2CN(AIBN)n-BuSnBrn-BuSnazobisisobutyronitrile radical initiator1-b1-cC-NH 2C-HRCH2 NH 2ArSO 2ClRCH2NH SO2Ar BuLiRCH2N SO2Ar(1).RCH2NH 2p-TsC

8、lBuLiLiAlH 4RCH2-HHinsbergs testOtosylamideRCH2-BuHNSO2ArLiAlH 4RCH2-Hp-TsClNaH NaHp-TsClCH3 S CltosylimideSO2 Ar(2).Ar-NH 2 Ar-HNH 2ClOSO2Arweaker C-N bond(3).(3).Ar-NH 2NaNO2H3PO2Ar-Hvia: ArNNH 2NaHAr N NHAr N NAr-HHCl- ArSO 2HJOC, 2001, 66, 8293.(4).-(4).RCH2NH 2 RCH2 NMe 3 XAg2ORCH2NMe 3OH-R=CH

9、2R-CH31-dC-SC-Hradical mechanismEtO 2CJOC, 1985, 50, 427.EtO 2CRaney Nickel: Ni - Al alloy, suspension(1).Raney Ni(2).Li / NH 3(3).L iAlH 4 / CuCl 2NaBH 4 / NiCl 2HN MeO 2CJCS Perkin Trans I, 1973, 654.N CH 2Ph OSRaney NiHN MeO 2CN CH 2PhHburn filter paper if dry mechanism uncertain, probably radica

10、lNaBHEt3 / FeCl2 (or CoCl2 , VCl 3)Chemistry: R-SH R-S-R R2SO R2SO2 R-SS-Rremove: Hg+; Ni1-eC=O C-HSHHS SRa(Ni)Hbest suitable for aryl ketone (ArCOR); not good for conjugate ketoneOBF 3,CH 2Cl 2 S H Hpreparation: HgCl 2 into ZnOH OHthioketal(1).Clemmensen reduction: Zn-Hg / HClsimilar: Sn / HCl SHac

11、idicC 6H 13thioketal: inert to LAH; react with RaNi; smell terrible and stay long; discard shoses(2).thioketal:SH / BF 3, CH2 Cl2 / RaNineutralO N NH 2OH-N N H HOH- HH(3).Wolff-Kishner reduction:N2H4, OH-, heatbasicON2H4N NN N H- N2(4).Pd-C / HCOPd-CPh Phmajor side-product: drawback of the reaction2

12、NH 4 : mild, efficient Ph PhHCO2NH 4(5).Tosylhydrazone reduction (Shapiro reaction):Synthesis, 2001, 16, 2370.H(modified Wolff-Kishner reduction):)TsNHNH 2 / REDN N Ts H-H for acyclic, may C=C side productO(6).enol derivatives:Tf 2O / N/ H2 / PtO 2Olimit: for -H compd.RED choice: MeLi; NaBH 3CN (goo

13、d) B H OLAH, NaBH 4: 2 group compete at Stanford U.B 2 H6 : very flamable, fire if shoot out from syringe(7).Et3SiH / CF 3COOHNO2Et3SiHPhCF3COOHNO 2 PhO OH2H O CF3 S O SCF3 H HJOC, 1973, 38, 2675.C C O ONOTfC CPtO2C C HPtO2 + H 2 = Pt1-fC=C C-C-Hcatalyst: Pd-CH2 PtO2H 2 , PtO2R RN TFA , 60 N(1).H 2

14、/ catPtO2 HORh-C; Rh-Al 2O3 ; OHHO HH OHin acetic conditionR = NHAc , NH 2(2).HN=NH (diimide)(3).B 2H 6 / RCO2H, heatRhCl(PPh3)3Nistereoselcetive: same side as OH (due to H bond)JOC, 1993, 58, 4979. RhCl(PPh3)3JOC, 2002, 67, 7890.CO2MeO RhCl(PPh3)3 OO benzene OCO2Me(4).n-Bu2SnI / MgBr 2-Et2O / H 3O+

15、O OWilkinsons catalyst: regioselective, prefer isolated double bond12 hrJACS, 1979, 101, 7020.Hvia:CH3CO2D Hsoluble in org solvent, 9 Ph group$ 50 / 25 gB RR Dprepare isotopeN2H2: unstable; generated in situ from DEAD (diethyl azodicarboxylate) or from: N2H 4 + H 2O2; N 2H4 + Cu(II) + O 2; NH2OH + N

16、H 2OSO3JCS, PT1, 1986, 546.EtO2CN N CO2EtOH-HO2CN N CO2HR RC C R RH N N H RO H H O- 2 CO2- N 2R C CR ROEtOn-Bu2SnI MgBr 2-Et2OH3O+ OEtOvia:N NO OOEtI OI OEtOsyn-addition H Hnot radical mech.JOC, 2001, 66, 8690.SnH R RH SnR R1-gC C NC-HCN: X (pseudo halogen), form KCN, NaCN with IA elements(1).K / Al

17、 2O3K / HMPAJOC, 1980, 45, 3227not quite same: not for H -R C C Ncharacteristcs: IR, CMR(2).Na / NH 3which is + ?HMPA: hexam ethylp hosphoramide (Me 2N) 3P=O= HMPT: hexam ethyl phosphoric t riamide (Me 2N) 3P=Otoxic?b.p. 230 Chighly toxic, cancer suspected agent?yes for white mouse, uncertain for hu

18、manmodified to: N N O1-hC CO2H C-HPh PhR OH solvent(1).particular structure:-CO2OPh NPh Ph- CO 2N Ph(2).normal structure: SOCl 2 / PhSeH / n-Bu 3SnHother Cl sources: PCl5; (COCl) 2oxalyl chlorideO R CO 2 R HR Rpyridinium betaine(3). organic electrochemistryCO 2He-OSOCl2O OPhSeH n-Bu 3SnHCO 2HRCH 2C

19、OHRCH 2C ClRCH 2 CSePhRCH 2 H(radical mechanism?)organoselenium chemistryCHOC-HOO H(1). RhCl(PPh 3) 3 (Wilkinsons cat)Cl PPh3RhPPh3 PPh3- PPh3Cl RhPPh3PPh3R C HR C PPh3RhPPh3(2). Rh(DPPD) 2+ Cl-oxidative additionClRHDPPD = Ph 2P-CH 2CH 2-PPh2ClRhrearrangementOCPPh3PPh3ClRreductive eliminationH+RhCPP

20、h3PPh3OC(O)X-CH 3OHSiEt 3 / B(C 6F5) 3R CH 3RClJOC, 2001, 66, 1672.1-i1-jRC-OR2-abRC-OH RC-(OR) 2dRC-HeRC=Cc RC(O)ORfRC-CN2-aRC-OH RC-ORapplication: for protecting groupgenerate H2, or butane gastrimethyloxonium tetrafluoroboratebase: NaH, n-BuLi, Ag 2OJOC, 1988, 53, 2985.JCS, 1930, 2166.Me group:(1

21、).-Me: base / CH3 -X RC-OCH 3(2).PhCHCH3 -X: CH 3I; CH 3 OSO2R; (CH 3)3O+ BFPhCH2-Cl4 , (CH 3)2SO4i.Williamson ether synthesis, SN2 typeii.not a good protecting group, too stable to convert back to alcoholBenzyl- group:2-: base / PhCH2 -XRC-OCH 2Ph = RC-OBZl = RC-OBnPhCH2 -X:PhCH2-Br: reactivity goo

22、dPhCH2-I: reactivity better than PhCH 2Br,i.abbreviation: benzyl = PhCH 2 = Bzl = Bnii.deprotecting: H 2 / Pd-C(3).allyl: base / BrRC-OCH 2CH=CH2(4).t-Bu: acid cat / RC-OtBuacid: H 2SO4H 3PO4 BF 3-Et 2Ogenerated in situ, PhCH2Br + NaICH3t-Bgroup:Willianson synthesis (base, SN2) not work: elimination

23、 side-product with base(5).trityl: py / Ph 3C-Br RC-OCPh3 = RC-OTrEt3N / TMS-ClCH 3 Si CH3ClCH 3SiClTrityl group: (tirphenylmethyl)i.SN1 reactionii.abbreviation: triphenylmethyl = trityl = -CPh 3 = -TrBr base(RO-Tr)(6).silyl: Et 3N / R 3 SiCl RC-OSiR 3(7).acetal / ketal: (see 3e)N/ TBDMS-ClN HTBDPS-

24、ClNO 2FNO 2CH 3PhSi ClPhiii.advantage: high MW, easy to handle (small amount become large amount) Silyl group:i.Willianson synthesis OK: Si - Cl bond longii.stability of silyl in acid/base: RC-O-TBDPS RC-O-TBDMS RC-O-TBS(8).ArF / CsF ROHCsF ROaromatic substitution reactioniii.abbrev.: TBDMS = tert-b

25、utyl-dimethylsilyl = TBS =2-bORRC-(OR) 2 RC-OR R ORORCH 2 ORRCH 2 OCH 2CH 2OHusually contain NO2, F as leaving groupactivator / hydride source RO(1).h / HSiCl 3(2).HCl / NaBH 3(CN)(3).AlCl 3 / LiAlH 4OCH 3OCH 3O OHClAlCl 3LiAlH 4OCH 3 HOHOOCH 32-cOR C ORRC-ORradical mechanism:SiCl 3t-BuORaNi with C=

26、SO(1).3hv / HSiClO O(2).HCl / tBu-OO- tBuJOC, 1974 , 39, 2470.HCltBu-OO-tBu(3).Lawesson reagent / RaNi(4).BF3 / NaBH 4limit for: lactoneOO Lawesson reagentSO RaNi OCH 3OS S OCH 3P PS S P SO ArOBF 3O ArLawesson reagent JOC, 1983 , 48, 1127.4 10ArNaBH 4O O Ar O2-dRC-HRC-OROHI 2 / Pb(OAc) 4O see mech-1

27、3O I HO I HO(1).I 2 / Pb(OAc) 4 / hvAngew Chem Int Eng., 1964, 8, 525. limit: for 56 ring neighboring OH grouphve / PtNO RMgBr N R(2).Organoelectro Chemistry: e - / Pt, R4NOTs N OHPhR4NOTsPhOH(79 %) Ph(3).NCS / MeOHJOC, 2002 , 67, 4498.H H H HOCH 3limit: for allylic alcoholN NH 2ON HNCS NOMeOH NHNH 22-e C CC-C-ORO C=C-ORO Hg(O CCF )O EtOHperacid:2-e.1 C CC CC-C-OR3 2 H+g OC CF3NaBH 4OEtCF 3CO3HCO 3Hgood resulti.Hg(OCOCF 3)2 ,