官能团最全转换

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　i5-7-gfedcbaedcbaihgfedcbahgfedcbahgfedcba6-4-3-1-2-ihgfedcbaC=C-C(O)-CH 3CH-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 CRCH 2 -SO 2 PhRC CHC CC-NH 2 ; C-NO 2C-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-OCH 2 ORC-NH 2C-ORC-HC-OHC=CC-HC(O)ORC-(OR) 2C-OHC-ORC-CHOC-CO 2 HC-CNC=CC=OC-SC-XC-OHC-HC=CjC(O)Xh C Njk C-HC-Br8-C-XiC-OHC-OHC(O)Z dcbaedcbafC-NH 2C-HjCX-CYC CXC=OhgfiC CHRCH(CO 2 H)-CH 3-C(O)-CH 3OOOXCRR"=CHXjC OC-NH 2C-CN9-C-CH 3C-XaeC=O

　1-adry pyridine:

　from CaH 2

　and distilled(an ester)triflatemesylatetosylateSOOO RCH 2 CF 3SOOO RCH 2 CH 3thiocarbonatedry PyCH 3CH 3CH 3OH(2). for 3" alcohol:LiAlH 4(1). for 1", 2" alcohol: C-H C-OH1- ihgfedcba C-CHOC-CO 2 HC-CNC=CC=OC-SC-NH 2C-XC-OHC-HO CSO PhSnBu 3CH 3CH 3CH 3Hn-Bu 3 SnH CSO Ph ClO CSO PhRCH 2 -HCH 3 SOOO RCH 2CH 3 SOOClRCH 2 OHsteric OKpurification textbook~ $ 30 / Kgtoluenesulfonyl chloride

　(s)methanesulfonyy chloride (l)~ $ 30 / KgjC(O)XPh 2 SiHCl / InCl 3 Ph PhHPhOHPhJOC, 2001, 66, 7741.ii. Ph 2 SiHCl / InCl 3i. p-TsCl // LiAlH 4i. ClC(S)OPh // n-Bu 3 SnHPhPhOCl 2 InCl SiPh 2Hvia:via:a unique Lewis acid catalyst, acceleratedeoxgyenationInCl 3indium trichlorideii. Et 3 SiH / Lewis acid J. Org. Chem. 2000, 65, 6179JOC, 2000, 65, 6179.CHCl 2rt, 3 hr

　1-bBu 3 SnH:

　(l), easy to removePh 3 SnH:

　(s), hard to removeMe 3 SnH:

　too volatile, toxic(AIBN)N NCN CN-

　N 2CNazobisisobutyronitrilen-BuSnHn-BuSnBrRn-BuSnBrRHRunstable in acid, form H 2

　gas;

　 stable in weak baseNaBH 3 CN:

　stable at pH 5-6hygroscopic, dried self, suggest: buy small amount each time(Grignard reagent)H 2 O Mg / Et 2 OJOC, 1969, 34, 3923.HBrNa / NH 3 ; Li / NH 3 ; Na / EtOHZn; Fe; Sn; Mg(3). metal reduction(2). hydride reduction(1). free radical reduction JACS, 1972, 94, 8905.C-H C-XAIBNn-Bu 3 SnHHBrradical initiatorNaBH 4

　/ InCl 3

　/ CH 3 CNradical

　reagentn-Bu 3 SnH / AlBNJACS, 2002, 124, 906.iiii

　NaBH 3 CNi

　LiAlH 4iiiii

　NaBH 4iiTHL, 1969, 3095.JOC, 1976, 41, 3064.iv

　LiBHEt 3

　 (super hydride)n-BuSnHn-BuSn

　mechanism uncertain, probably radicalburn filter paper if dryRaney Nickel:

　Ni - Al alloy, suspensiontosylimidetosylamideJCS Perkin Trans I, 1973, 654.(3).

　LiAlH 4

　/ CuCl 2NaBH 4

　/ NiCl 2NaBHEt 3

　/ FeCl 2

　(or CoCl 2 , VCl 3 )(2). Li / NH 3(1). Raney NiNSO 2 ArSO 2 ArRCH 2RCH 2 N SO 2 Ar- BuHRCH 2 NH SO 2 ArBuLiLiAlH 4RCH 2 -HCH 3 SOOClRCH 2 NH 2BuLi1-d1-cC-H C-SLiAlH 4C-H C-NH 2RCH 2 -HRCH 2 NH 2Hinsberg"s testradical mechanismweaker C-N bondChemistry: R-SHR-S-R R 2 SOR 2 SO 2R-SS-Rremove:

　Hg + ; Ni(1).(2).Ar-HNaNO 2HClH 3 PO 2Ar-NH 2RCH 2 NH 2 RCH 2 NMe 3R=CH 2 R-CH 3(4).X -RCH 2 NMe 3 OH -Ag 2 OJOC, 1985, 50, 427.p-TsClNaH NaHp-TsClNH 2 Clvia:NNH 2SO 2 ArArNaHN NH Ar N N Ar Ar-H- ArSO 2 H(3).Ar-NH 2Ar-Hp-TsClJOC, 2001, 66, 8293.ArSO 2 ClRaney

　 NiN HNS MeO 2 CCH 2 PhEtO 2 CON HNH MeO 2 CCH 2 PhEtO 2 C

　for acyclic, may C=C side productbasicneutralacidicHHH -N N TsCH 2 Cl 2C=OC-H 1-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/ BF 3 , CH 2 Cl 2

　// RaNiN 2 H 4 , OH - , heatTsNHNH 2

　// REDlimit:

　for -H compd.HHRa(Ni)BF 3 ,SSHHSSHHOthioketal:

　 inert to LAH; react with RaNi; smell terrible and stay long;

　discard shosesthioketalmajor side-product: drawback of the reactionN N- N 2OH -H N NHN N HOH -N NH 2N 2 H 4OHHNCHCOCF 3 SOOO SOCF 3OC COTfH 2PtO 2C CH HHTf 2 O / N// H 2

　/ PtO 2LAH, NaBH 4 :

　2 group compete at Stanford U.B 2 H 6 :

　very flamable, fire if shoot out from syringeOOB Hbest suitable for aryl ketone

　(ArCOR); not good for conjugate ketone preparation:

　HgCl 2

　into ZnRED choice:

　MeLi; NaBH 3 CN

　(good)PtO 2

　+ H 2

　= PtOH OC 6 H 13similar: Sn / HCl(4). Pd-C / HCO 2 NH 4 :

　 mild, efficientPh PhOPh PhSynthesis, 2001, 16, 2370.HCO 2 NH 4Pd-C(7). Et 3 SiH / CF 3 COOHPhONO 2Ph NO 2JOC, 1973, 38, 2675.CF 3 COOHEt 3 SiH

　HOOHHHPtO 2H 2HOOH$ 50 / 25 gJOC, 1993, 58, 4979.syn-additionprepare isotopeCH 3 CO 2 DHDC=C C-C-H1-f(1).

　H 2

　/ cat(2).

　HN=NH

　(diimide)(3).

　B 2 H 6

　// RCO 2 H, heatWilkinson"s catalyst:

　regioselective, prefer isolated double bondsoluble in org solvent, 9 Ph groupstereoselcetive:

　same side as OH (due to H bond)catalyst: Pd-CPtO 2Rh-C; Rh-Al 2 O 3 ; RhCl(PPh 3 ) 3NiOORhCl(PPh 3 ) 3N 2 H 2 : unstable;

　generated in situ from "DEAD"

　(diethyl azodicarboxylate)

　 or from: N 2 H 4

　+ H 2 O 2 ; N 2 H 4

　+ Cu(II) + O 2 ; NH 2 OH + NH 2 OSO 3via: HB RRN N CO 2 Et EtO 2 CN N CO 2 H HO 2 COH -- 2 CO 2N NOOHOOHN N H H- N 2C CRRRRC CRRRRH HJCS, PT1, 1986, 546.OOCO 2 MeOOCO 2 MeRhCl(PPh 3 ) 312 hrJACS, 1979, 101, 7020.NRNRH 2 , PtO 2TFA , 60 ℃R = NHAc , NH 2JOC, 2002, 67, 7890.in acetic conditionbenzene(4). n-Bu 2 SnI / MgBr 2 -Et 2 O // H 3 O +OEtOH 3 O +OEtOMgBr 2 -Et 2 On-Bu 2 SnIJOC, 2001, 66, 8690.OSnHOEtIR ROOEtSnIRH Rvia:not radical mech.

　pyridinium betainesolventNPhPh PhRR HNPhPh PhRR CO 2- CO 2b.p. ~ 230 Chighly toxic, cancer suspected agent?=

　HMPT: hexamethylphosphoric triamide

　 (Me 2 N) 3 P=Otoxic?characteristcs:

　IR, CMRwhich is  +

　?C C R Nnot quite same:

　not for H -e -CO 2 HCO 2 H(3). organic electrochemistry-CO 2 (1). particular structure: C-H1-g(1). K / Al 2 O 3

　 K / HMPA(2).

　Na / NH 31-h(2).

　normal structure:

　SOCl 2

　// PhSeH // n-Bu 3 SnHC C NJOC, 1980, 45, 3227CN:

　~ X

　(pseudo halogen),

　form KCN, NaCN with IA elementsHMPA:

　hexamethylphosphoramide

　(Me 2 N) 3 P=Oyes for white mouse, uncertain for humanmodified to: NNOC CO 2 H C-HCOSePh RCH 2 RCH 2 HCOOH RCH 2COCl RCH 2PhSeHn-Bu 3 SnH SOCl 2(radical mechanism?)other Cl

　sources:

　PCl 5 ; (COCl) 2oxalyl chlorideorganoselenium chemistryOHORO

　1-iCHO C-H(1).

　RhCl(PPh 3 ) 3

　 (Wilkinson"s cat)(2).

　Rh(DPPD) 2 +

　Cl -oxidative additionrearrangementreductive eliminationRhPPh 3PPh 3 CClO+ R HRhPPh 3PPh 3 CROClHRhPPh 3PPh 3ClHR COR COHRhPPh 3PPh 3Cl- PPh 3ClRhPPh 3PPh 3 PPh 3DPPD

　=

　Ph 2 P-CH 2 CH 2 -PPh 21-jC(O)X -CH 3R ClOR CH 3HSiEt 3

　/ B(C 6 F 5 ) 3JOC, 2001, 66, 1672.

　OOOOHAlCl 3LiAlH 4activator / hydride sourceH OCH 3HClOCH 3OCH 3OCH 3RCH 2

　OROORRORORRCH 2

　OCH 2 CH 2 OH(3).

　AlCl 3

　/ LiAlH 4(2).

　HCl / NaBH 3 (CN)(1).

　h / HSiCl 3RC-(OR) 2 RC-OR 2-bSiPhPhClSiCH 3CH 3ClCH 3 SiCH 3CH 3ClNNH/ TBDMS-ClTBDPS-ClEt 3 N / TMS-Clacid: H 2 SO 4H 3 PO 4BF 3 -Et 2 ORC-OCH 2 CH=CH2RC-OCPh 3

　= RC - OTrRC-OtBuRC-OCH 3RC-OSiR 3RC-OCH 2 Ph

　= 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.

　S N 1 reactionii. abbreviation: triphenylmethyl

　=

　trityl

　=

　-CPh 3

　 =

　-Triii. advantage:

　high MW, easy to handle

　(small amount become large amount)base BrWillianson synthesis

　(base, S N 2) not work:

　elimination side-product with baset-Butyl group:i.

　abbreviation:

　benzyl

　=

　PhCH 2

　 = Bzl

　=

　Bnii. deprotecting:

　H 2

　/ Pd-CPhCH 2 -ClPhCH 2 -Br:

　reactivity goodPhCH 2 -I:

　reactivity better than PhCH 2 Br,

　 generated in situ, PhCH 2 Br +

　NaIPhCH 2 -X: Benzyl-

　group:i.

　Williamson ether synthesis, S N 2 typeii.

　not a good protecting group, too stable to convert back to alcoholMe group:CH 3 -X:

　CH 3 I; CH 3 OSO 2 R;

　(CH 3 ) 3 O +

　BF 4 - , (CH 3 ) 2 SO 4base: NaH, n-BuLi, Ag 2 O(4). t-Bu:

　acid cat / (3). allyl:

　base / Br(6).

　silyl:

　Et 3 N / R 3 SiCl(5). trityl:

　py // Ph 3 C-Br(2). PhCH 2 -:

　 base / PhCH 2 -Xapplication:

　for protecting groupedcba 2-RC=CRC-HRC(O)ORRC-(OR) 2RC-OHRC-ORRC-OH RC-OR(1). Me:

　 base / CH 3 -X2-a(7).

　acetal / ketal:

　(see 3e)f RC-CNgenerate H 2 , or butane gasJOC, 1988, 53, 2985.trimethyloxonium tetrafluoroborateJCS, 1930, 2166.(8).

　ArF / CsFROHFNO 2RONO 2aromatic substitution reactionusually

　contain NO 2 ,

　F as leaving groupCsF

　see mech-13hvI 2

　/ Pb(OAc) 4

　O OHO IHOHOIlimit: for 5~6 ring neighboring OH group(1). I 2

　/ Pb(OAc) 4

　/ hvradical mechanism: SiCl 3t-BuORaNi with C=SJOC, 1983, 48, 1127.JOC, 1974, 39, 2470.RaNiLawesson reagentSO OOO~

　P 4 S 10tBu-OO-tBuHClOOOR COOR2-cRC-OR2-dRC-ORRC-H(1).

　hv / HSiCl 3(2).

　HCl / tBu-OO-tBu(3).

　Lawesson reagent / RaNi(4).

　BF 3

　/ NaBH 4PSPSSSOCH 3CH 3 OOOOOArArOO ArArBF 3NaBH 4Lawesson reagent(2). Organoelectro Chemistry: e -

　/ Pt, R 4 NOTs NOHPhNOPhe / PtR 4 NOTs(79 %)NOHPhR"R"MgBrAngew Chem Int Eng., 1964, 8, 525.limit for: lactoneHNNHNH 2OH HHNNHNH 2OOCH 3 NCS(3). NCS / MeOHMeOHJOC, 2002, 67, 4498.limit: for allylic alcohol

　C-C-OR2-eC CC CONaBH 4OEtCO 2 EtOHCO 2 EtH HOHHOHOOi. Hg(OCOCF 3 ) 2 , ROH // NaBH 4i.

　peracidii. via halohydrin:

　HOBr, H 2 O // K 2 CO 3iii. Sharpless asymmetric epoxidation:

　 t-BuOOH, Ti(OiPr) 4

　// (+)-diethyl tartrateHg(O COCF 3 ) 2OOmCPBAH 2 OHOBrBr BrOHtrans-diaxial attack!Olimit for allyl alcohol, high e.e.Sharplessstereoselectiveracemic productsHg O+COCF 3racemic productsHOBr generation: NBS + H 2 O + DMSOOOconversion: HOAcOHOAcOSO 2 MeOAcEtOHC=C-ORC=C-ORC-C-ORC CC CC CC CO2-e. 12-e. 22-e. 3ii. HCHOPrins RxnOSO 2 MeOHO OOHOH OHHCHO (aq)O Ovia:H 2 O HCHOSynthesis, 1980, 871.CO 3 HCO 3 HClCF 3 CO 3 HCO 3 HCO 2 Hgood resultperoxybenzoic acidMCPBA(m-chloroperoxybenzoic acid)stable solid, 85 % (contain MCBA) for safetyperacid:iv.

　t-BuOOH, Mo(CO) 6v.

　KHSO 5vi.

　H 2 O 2 , t-BuOH, MnSO 4

　// NaHCO 3 , pH 8JACS, 2001, 123, 2933.HO 2 CHO 2 COnew, cheap,, simple, green chemistrypotassium hydrogen preoxideconvenient, inexpensive, powerful. JOC, 1980, 45, 4758. JOC, 1982, 47, 2670.OOHOOBr 2via:Br 2

　/ ROHOOBrHHeterocyclic Chem, 1990, 27, 583.C-C-OR 2-f C N CROH / HClEt C N Et COEtOEtOEtEtOHHClJACS, 1942, 64, 1825.(+)-diethyl tartratechiral sourceJOC, 2001, 66, 521.

　C-OHC-HC-ORC-NH 2C-X3- abcd3-aC-OH C-HOH(1). [PhI(OAc)-O] 2 -Mn(TPP)(2). organic electrochemistry[PhI(OAc)-O] 2 -Mn(TPP)JACS, 1983, 105, 3515.JACS, 1983, 105, 2920.NO 2NH 2OHe -H 2 O(3). X 2

　/ hv // OH -indirectHOHOHOOHHOH3-a. 13-a. 23-a. 3HROSeOROHSeHOORSeOHROHSe(OH) 2H 2 ORHROHSeO 2JACS, 1972, 94, 7154.SeO 2for allyl H:(1) Me 3 SiCl // MPCBA//H 3 O +(2). O 2 , LDA, (EtO) 3 PROCO 2 RROCO 2 ROHO OROROOPOEtOEtvia:JACS, 1975, 97, 6909.PhOPhOSiMe 3OPhOSiMe 3PhOSiMe 3OHOHPhOOH1. Me 3 SiClMCPBAJOC, 1975, 40, 3427.H 3 OO 2 , LDA,(EtO) 3 PPhOPhOOH2. MCPBAMe 3 SiClihgfeC=OC---OHC-OC(O)RC-OCH 2 ORC=CjC O

　(1). Me:

　application:

　deprotecting(2). PhCH 2 - (5). trityl:

　(6).

　silyl: (3). allyl:

　(4). t-Bu:

　RC-OCH 2 Ph

　= RC-OBZl

　= RC-OBnRC-OSiR 3RC-OCH 3RC-OtBuRC-OCPh 3

　= RC-OTrRC-OCH 2 CH=CH 2C-OH C-ORNi.

　TMSIii. BF 3 -Et 2 O // R-SH (or HS-CH 2 CH 2 -SH)iii. BBr 3

　/ CH 2 Cl 2 , 0-10 C/ LiI, heatvi. RCH 2 -OHRCH 2 -O-SiMe 3Me 3 Si-IRCH 2 OCH 3SiMe 3- CH 3 IRCH 2 -O-CH 3I -- I -RCH 2 -O-CH 3RCH 2 OCH 3BF 3BF 3- RSCH 3RSHRCH 2 -OHOCH 3OH+heat- CH 3 Cli.

　H 2

　/ Pd-Cii. CNCNClClOO, OH -[O]OH- tolueneOH -OHO C OCH 3OO CH 2 OCH 3H 2

　/ Pd-CO CH 2RhCl(PPh 3 ) 3 , H 3 O +- EtCHO- Ph 3 COHHOAcHOHHO CPh 3- Me 3 CCF 3 CO 2 HOH OH 3 O +RhCl(PPh 3 ) 3HOHHOHOi.

　TFA (CF 3 CO 2 H)ii. HBr / HOAciii. TMS-Ii.

　HOAc:

　weak acid: good leaving groupii. H 2

　/ Pd-C:

　reserve, too strong, might affect other groupneed stronger acidi.

　F -

　: HF, Py-H +

　F - ;

　n-Bu 4 N +

　F -ii.

　mild base:

　not for TBDPSiii. mild acid: only for TMS, not for TBDMS, TBDPS-SiMe 3-SiBuMe 2-SiBuPh 2Si - F:

　140 Kcal/molif HOBr:

　OK for TMDMS JOC, 1987, 52, 4973.OCOCF 3+JOC, 1973, 38, 3224.iv. AlCl 3

　/ RSHTHL, 2001,

　42,

　9207.MeO CO 2 MeHO CO 2 MeCH 3 (CH 2 ) 11 SHodorlessAlCl 3v. / heatCl -NH3-b NH Cl -triphenylmethylorganic base:

　TMGORCH 3 CNNHNNOHR = TBDMS, TBDPS, AcTMG1h1,1,3,3-TetramethylguanidineTMG:Organic Letters, 2003, 5, 209.

　3-c(1). HNO 2

　// H 3 O +C-OHC-X(1). OH -(2). KO 2

　/ DMSO3-d C-OH C-NH 2not practically useful: R-OH cheaper than R-XJOC, 1975, 40, 1678.(2). Na 2 [Fe(CN) 5 (NO)] / K 2 CO 3

　/ H 2 ONO +H 3 O +OHN 2 + X - NH 23-eR-OH R-OC(O)R(1).

　Symmetry:ketal:

　use H 3 O +acetal: use H 3 O +(2).

　unsymetry: RO-MOMRO-MEMRO-MTMRO-THPMeOH+H 3 O +OHHOMeOMe+OH HOH 3 O +OO Oi. H 3 O + ;

　ii.

　HCl / MeOH;

　iii.

　BBrMe 2p-TsOH / MeOH i. H 3 O + ;

　ii.

　ZnBr 2

　/ CH 2 Cl 2 ;

　iii.

　BBrMe 2HgCl 2

　/ CH 3 CN (aq.)actually, acetal exchange rather than hydrolysisH 3 O +RO-HRO-HRO-HRO-HRO-CH 2 SCH 3RO-CH 2 OCH 3R OOSO 3 HOCH 3 OCH 2 ClCH 3 OCH 2 CH 2 OCH 2 ClCH 3 SCH 2 Clp-TSOHOp-TSOHCSA

　(camphorsulfonic acid)(p-toluenesulfonic acid)SO 3 H CH 3or CSARO-MOM

　highly toxic, world top 10 killer, discardnot toxicnot dangerousTHP:

　tetrahydropyranRO-CH 2 OCH 2 CH 2 OCH 3JOC, 1984, 49, 3912.(3). Ag 2 O / H 2 OH 3 O +H 3 O +H 3 O +THL, 1975, 3183.JOC, 1986, 51, 3913. RO 2 C(CH 2 ) 3 CHRNH 2RO 2 C (CH 2 ) 3 CHROHNa 2 [Fe(CN) 5 (NO)]K 2 CO 3

　/ H 2 O

　 3-f(1).

　base:

　KHCO 3

　(or K 2 CO 3 , NH 3 ) /

　MeOH;

　 NaOH (1 %, or 0.5 N)(3).

　RED: (2).

　acid:

　H 3 O +PPh 3

　/ DEAD / RCO 2 H // OH -3-gR" C O ROR OHC OH C OHMitsunobu inversion

　Synthesis, 1981, 1.JOC, 1987, 52, 4235.common esters: formate

　=

　HCO 2 R

　 ------------------------

　 KHCO 3

　(or K 2 CO 3 , or NH 3 ) / MeOHtrifluoroacetate

　=

　CF 3 CO 2 R

　 ------------

　KHCO 3

　(or K 2 CO 3 , or NH 3 ) / MeOHacetate

　=

　CH 3 CO 2 R

　=

　ROAc

　---------

　KHCO 3

　(or K 2 CO 3 , or NH 3 ) / MeOHbenzoate

　=

　PhCO 2 R

　=

　ROBz

　--------

　NaOH (1 %) / MeOHpivalate

　=

　tBu-CO 2 R

　=

　ROPv

　------

　NaOH (0.5 N) / EtOH(or K 2 CO 3

　/ MeOH)MeOHMeOHP-TsOHLAHHClOOOHO OHOHOOHOOOOselectivity:PPh 3

　/ DEADR-O-H***PhCO 2 HN NH CO 2 Et EtO 2 CP Ph O RPhPhOH -Ph C OROHOPhCO 2 H**HOPPh 3N NH CO 2 Et EtO 2 CPPh 3ROHEtO 2 C N N CO 2 Eti LiAlH 4ii. NaAlH 2 (OCH 2 CH 2 OCH 3 )CH 3 O 2 CCO 2 CH 3HOOHNaAlH 2 (OCH 2 CH 2 OCH 3 ) 2C 6 H 6 ,

　r.t.hydride:electron:Na / NH 3 AGIEE, 2002, 41, 3028.

　regioselectivity determined by reactivity.

　reactivity:

　 ald

　>

　ketone

　>

　estergenerate acetoneopposite to Oppenauer oxidationJCS, 1969, 1653. JCS, 1970, 785.JACS, 1972, 94, 7159.OIrCl 4Al(OiPr) 3O+AlOiPrOiPrOHLAHOOOOHHHO Al(OiPr) 2IrCl 3OHHOHHOHLAH

　------------

　almost all:

　ald, ketone, acie, ester, acyl X, anhydrideNaBH 4

　 ---------------

　not for acid, ester

　 (but LiBH 4

　work for ester)B 2 H 6

　 ---------------

　not for ester, acyl X, anhydride;

　 from top:

　LiAlH 4 ;

　NaBH 4 ;

　Na / NH 3Al (OiPr) 3

　/ iPrOH

　 -----------

　 Meerwein-Pondorf-Verley rxnIrCl 4

　/ iPrOH / P(OMe) 3

　------

　 Henbest rxnLiBH(secBu) 3

　 ------------------

　H. C. Brownfrom bottom:C OH C O(2).

　stereoselective: (1).

　regioselective:

　3-h(3).

　HCHO reagent: Me CHOMeOHHCHOKOHJACS, 1935, 511, 903.CH 3 CHOC(CH 2 OH) 4HCHOCa(OH) 2Org.Syn, 1925, 4, 53.HCHO / KOHHCHO / Ca(OH) 2Synthesis, 1994, 1007.PhNO 2OPhNO 2H OHBH 3

　/ SMe 2JOC, 2001, 66, 7514.JOC, 2003, 68, 2030.OOHBH 3

　/ THFreflux 5 d99.5 % transsolvent: THF, SMe 2C OH C O3-iR 3 B, HOCH 2 CH 2 OH // H 2 O 2

　// NaOHJOC, 1986, 51, 4925.C O R B C ORRR 3 BB CRRROR B CORRR 3 C B OHOCH 2 CH 2 OHR 3 C BOOH 2 O 2OHR 3 C BOOO O HO BOOR 3 CH 2 OR 3 C OHO OHOHNaBH 4

　/ CeCl 3NaBH 4+99%trace51%49%[H]JACS, 1978, 100, 2226.Luche ReductionTHL, 2000, 41, 5631.influence of the lanthanide on the regiochemistry

　p pr ra ac ct ti ic ce e 3-kOOHOHOHOHOOHOHOHOHOHPd-CH +OOHOHOHOHO OHOHOHOHOHH 2PyCrO 3Ph 3 C-ClOH OTrOBnOBnBnOOBnLAHH 3 O +OH OHOBnOBnBnOOBnPhCH 2 -BrOHOOBnOBnBnOOBn HOOHBnOOBnOBnOBnO OMeOBnOBnBnOOBnMeOHO OMeOHOHHOOHO OHOHOHHOOHchemistry:hemiacetalROH ROBnROHROHROTr ROHJOC, 1967, 32, 3452.1", 2" alcoholO OTrOBnOBnBnOOBnH 2 O 2 :

　dangerous,

　 skin whiten, metal decomposeHg (OAc) 2 :

　toxic, hard to removeH 2 OOHOBR 2OH - (40%-60%)H 2 O 2HBHBB 2 H 6NaBH 4H 2 OHg(OAc) 2CH CRR RH OHCH CRROHRHgOAcRCH CRRC OH C C(3). B 2 H 6 , H 2 O 2

　/ OH - , H 2 O(2). Hg(OAc) 2 , H 2 O // NaBH 4(1).

　H 3 O +3-jO O HBRRC OH C C3-j. 1C C3-j. 2 hydroboration:

　 oxymercuration - demercuration:

　hydration:

　C COH OH(1). KMnO 4

　/ NaOH(2). OsO 4(3). H 2 O 2 /HCO 2 H(4). Na / EtOHOHOHOHOHcistrancis

　+ tranJACS, 1945, 67, 1786.Ann, 1949, 561, 165.JCS, 1946, 2988.cis

　N CH 3ClHN CH 3ClHMe 2 NNNCH 3HClN CH 3HHhN CH 3HHN CH 3ClHH +NCSN CH 3Cl NHCH 3NHCHOMe 2 NNTsOCNHCHOTsODMFMe 2 NHHCOOHAcOHOAcTsClMeOHK 2 CO 3NHCHO2. H 2

　/ Pt1. LAHR 3 C NH 2R C NR 2R C NHRR 3 C OHR 2 C OHRCOHR C NH 2tertiarysecondaryprimaryCompare nomenclature class:not a very useful reactionC-NC-HC-NC-XC-OHC=OC=C4- abcdefg4-aC-NC-H(1). nitrene insertion process:

　PhI(OAc) 2

　/ Fe

　(TPP)Cl(3). nitrogen cation radical

　(via Hofmann - Loeffler - Freytag)SO 2 NH 2 Ph IOAcOAc SOONHSOON I PhFe

　(TPP)ClSOONH 2(insertion)TPPN NN NPhHCOOHAcONH 2Me 2 NMe 2 NNNCSH 2 SO 4hJACS, 1959, 81, 5209.2. NaN 3CON N NN C O1. SO 2 Cl 2HOAc H 2 ON COOHCO 2NH 2CH 3COCHO OhiC N(2). PhI=NTsNHTsPhI NTsRu

　catJOC, 2000, 65, 7858.C(O)XC-C(O)X

　RC N Z RC NH 2NH 2NH 2RC NO 2RC N 3RC N MeRC N CPhRC N CPh 3RC NH 2RC NH 2RC NH 2RC NH 2RC NH 2iiiiiiRC N COOtBuRC N COOPh RC NH 2RC NH 2C-N C-NH 2 4-bCF 3 CO 3 H // Fe / HOAc1. many reducing agents1. NaBH 4 ;

　2. Al (Hg)H 2 O 2

　// Ac 2 O, heat / H 3 O +H 2

　/ Pd-C1. HOAc; 2. H 2

　/ Pd-C1. TFA; 2. HClH 2

　/ Pd-CNH 2 NH 2 NO 2H--HNO 2NOO+HNH 2NH 2CF 3 CO 3 HFe/HOAcspecial case, limit for axial to equitorial NH 2- HCHONHNOHNAc2OR CHHN N N+HR CHHNH N NRCH 2 NH 2N 2NCH 3NHN CH 3N CH 3O

　1. H 2 O 22. Ac 2 O3. H 2 ONHOOH 2

　/ Pd-CNHCH 2 PhNH 2N CH 2 OCH 3NHTFANH 2NH 2O C OON CPhCN(CH 3 ) 3 CNHCOOtBuNH 2Cl C OOCH 2 PhBOC ONNHCOOCPhNH COOHNH 2 H 2 /catCO 24-b.14-b.2[BOC-OFF]THL, 1975, 4393.BOC-ON [58632-95-4]: 2-(t-butoxycarbonyloxyimino)-2-phenylacetonitrile$ 300 / 100 gNH-BOCCO 2 EtNH 2CO 2 EtBOC-ONN-oxideapplication:.D --amino acidCO 2 HNH 2 RHHR N 3CO 2 EtNaN 3- TPPBF 4 -NPhPh PhHR CO 2 EtL --amino acidHR CO 2 HNH 21. reduction2. hydrolysis(S N 2)2. organic electrochemistry1.2.3.4.Fe 3 (CO) 12

　/ CH 3 OH JOC, 1972, 37, 930.NO 2NH 2Fe 3 (CO) 12

　/ CH 3 OH reflux

　 8 hrNaBH 4

　/ Pd-CNa 2 SSn / HClVogel"s

　12.57Vogel"s

　12.58Vogel"s

　12.59NO 2OCH 3NH 2OCH 3Eg-NiDMFrt. 15 hrJOC, 1999, 64, 2301.Eg-Ni:

　electrogenerated nickelC NH 2 C NH 25.H 2

　/ Pt (S)-CJACS, 1965, 87, 2767.sulfided platium not affect: aromatic rings, ketones, halides, nitriles, amide, easters

　HC(OEt) 3

　becomes HCO 2 Etnew: p-TsOH / HC(OEt) 3

　/ EtOH, reflux 5 hrCH 3 COCH 3OOOOOEtOEtCO 2 EtHHOHHOCO 2 Etold:

　FeCl 3 , MgSO 4

　in Soxhlet extract, reflux 40 hrabout HC(OEt) 3 :

　ethyl orthoformate

　($ 25 / 1 L), may function as dehydrating agentJACS, 1933, 55, 4579.HCO 2 HHCHO NMe 2CO 2 EtNH 2CO 2 EtH C OO-CO 2NCH 3CH 3NH 2H C HONCH 3HHNHCH 3H C OO-CO 2H C HON CHHHH -HC(OEt) 3R NH 2R NHOEtOEtR N CH OEtH -R NH CH 2OEtR N CH 2R N CH 3HC N R Z C N R R"RC NCC N RCCRC NH 2iC N R N N+ -C N R R" ii1. HCHO / HCO 2 H1. RBCl 2

　/ base1. HC(OEt) 3

　// NaBH 4 ;

　2. R 2 CO // NaBH 3 CNNH 2NCH 3CH 3HCHOHCOOHN 3NHBCl 2NH 2COOHNCOOHHCH 3HC(OEt) 3 NaBH 44b.32. HCHO // H 2

　/ Pd-CN 3 NO 2MeO 2 CNaBH 4CoCl 2 - 6H 2 O

　(cat)rtNH 2 NO 2MeO 2 CSynthesis, 1979, 537.mild conditionhigh yieldnot affect:: NO 2 ,

　C=C,

　CN,

　COOR, COOH2. NaBH 4

　/ CoCl 2 - 6H 2 O 原甲酸三乙酯NRHNBClClRNN NBRClClR-BCl 2 NN N- N 2

　OHNOOKnot good, usually contain polyalkylation products1. Gabriel:2. Delepine3. NaN 3

　/ REDTSClN 2 H 4NH 2in fact: C-OH

　 C- OTs

　 C-NH 24-dC-N C-OHNOCH 3OCH 3HSPh-N 2MgBrOMeOMeNOCH 3OCH 3N NSPhPhS N N NNH 2OCH 3OCH 3BrOMeOMe+ + (PhCH 2 ) 3 N (PhCH 2 ) 2 NH PhCH 2 NH 2Ph CH 2 NH 2N N NNCH 2 PhN N NNPh CH 2 BrPh CH 2 Br4-c5. Unpolung4. NaN 3

　/ RED3. Delepine2. Gabriel:1. NH 3C-NC-XNOOKN 2 H 4NNNNH 2 Oi. LAH, NaBH 4ii. H 2

　/ catiii

　Zn / HCl; Al (Hg)i. Mg // NH 2 Clii. Mg // PhSCH 2 -N 3

　 //

　KOHcommercial available, tetramer of Me 3 NBr -NNNNCH 2 Ph6. CH 3 NH 2

　(aq) / EtOH // HCl / Et 2 OJOC, 1988, 53, 2918.OClONHMeCH 3 NH 2

　/ EtOHHCl / Et 2 ONH 2 Cl MgR NH 2 R MgBr R BrOONHNH 2NHNH 24. CBr 4 , PPh 3 , NaN 3 , DMF // PPh 3

　/ THFJOC, 2000, 65, 7110. N ROHN RBrN RN N NN RNH 2CBr 4PPh 3NaN 3 PPh 3THFGabriel amine synthesisN 2 H 4Ph CH 2 NH 2 NOOCH 2 PhPh CH 2 BrNOOKNNNNurotropine (乌洛托品)methenamine (六甲烯胺)hexamethylenetetramine (环六亚甲基四胺)内服后遇酸分解出 HCHO,可做尿道消毒剂, 治膀胱炎

　CH 3 CN:

　 bp 81-2, mp -48;

　polar solvent, for UV, HPLC, NMR (CMR very high field 0.86 ppm, ring current)immonium saltB 2 H 6

　/ H 2 NOSO 3 HB 2 H 6

　/ H 2 NONHB RRNH 2NH 2 ClH 2 OB 2 H 6BBRRNHClN C CH 3H+N C CH 3OHNH COCH 3H +3CH 3 CNCH 3 CN / H 3 O +B 2 H 6

　/ NH 2 ClC=C C-C-NHCOCH 3C=C C-C-NH 2C=C C-C-N4-fNHH HN NHPhHHLiAlH 4NHN N NHHN N NONSiMe 3N NN N NNH 3CO 2HOO -NH 2 NH 2ONaBH 3 CNPH 6CH 3 NH 2acidNH CH 3N CH 3 ONH 3RaNi / H 2NH 2OLiAlH 4Me 3 SiN 3NH 2O SiMe 3OAl (Hg)PhNHNH 2N NHPh Oreductive amination!Leuckart reactionmost generalcatalytic reductive aminationvia:

　acetal / ketal type exchangevia: hydrazoneC=O C-N4. PhNHNH 2

　// Al (Hg)2. Me 3 SiN 3

　// LiAlH 43. NH 3

　(excess) // RaNi / H 21. RNH 2

　// NaBH 3 CN5. NH 4 + HCO 2 -4-e(radical)6. RNH 2

　/ n-Bu 2 SnClH / HMPASynthesis, 2000, 789.Ph CHOPh NHPhvia:Sn HByByNPhPhOP(NMe 2 ) 3ClPhNH 2

　n-Bu 2 SnClHHMPA

　not for B 2 H 6 , affect C=C2. NaBH 41. Et 3 O + BF 4 -NH5. P 4 S 10

　 // RaNi4. Et 3 O +

　BF 4 -

　 // NaBH 43. B 2 H 62. NaBH 3 (OCOR)1. LiAlH 4R CH 2 NHRR CONHRRaNiNHNHSNHONNOEtHHNOEt-

　Et 2 ONHONH NHO2. NaBH 41. Et 3 O + BF 4 -NHOEt 3 O + BF 4 -HNHH- EtOH[Sulfide]6. Lawesson"s reagent

　// RaNi4-hEt 3 O + :

　 Et source, convert to good leaving group; not use

　EtBrdifferent from: HC(OEt) 3

　 dehydrating agent;

　 H 2 C(OEt) 2

　(ketal agent) NCO 2 HOHNHOHLiAlH 4THFJOC, 1985, 50, 1711.CH 3 CONH CO 2 CH 3 CH 3 CH 2 NH CO 2 CH 3B 2 H 64-g4-g.a4-g.bR C NR C NH 2R C NH 2R"R C NH 2R C NH 2R"formformAlH 3

　/ THFBrCNBr NH2JOC, 2000, 65, 8152.AlH 3THFTH, 1989, 30, 5137.JOC, 1987, 52, 3901.R"Li // NaBH 4R"MgX // NaBH 4R"MgX // Li/NH 3 (l)R" 2 CuLi // NaBH 4TH, 1989, 30, 5139.JOC, 1993, 58, 4313.R C NR C NH 2R"R"M // H

　not good, lots of side-products, Br 2

　strong oxidantmost usefultoxic, Schmidt died of itH 2 O from outsideH 2 Oanti-migrationJACS, 1981, 103, 7368.Application:OCO 2 EtCO 2 EtCO 2 HCO 2 HCO 2 EtCO 2 EtOH -H 2

　/ Pd-Cn-Pr 3 Al80 C。NNHN+CO 2 HCO 2 H1.NH 2 OH2.TsClBeckmannHofmannCurtiusSchmidtR CH 2 COOH R CH 2 COCl R CH 2 CONH 2R CH 2 NH 2Br 2R CH 2 CONH-BrHN 3NH 3R CH 2 CON N NSOCl 2NaN 3R CH 2 CON N NN-BrOC CH 2 ROH -R CH 2 N C OH 2 OR CH 2 COCH 3R CH 2 C CH 3NOHR CH 2C CH 3NOTsR CH 2 N C CH 3 R CH 2 N C CH 3HOCOCH 3 RCH 2Beckmann:

　NH 2 OH // TsCl / H 2 OCurtius:

　NaN 3

　 // H 2 O 2. Schmidt:

　HN 3

　 //

　H 2 O 1. Hofmann:

　SOCl 2 , NH 3 , Br 2

　/ OH -

　/ heatRCH 2 COZR CH 2 NH 24-iCOCl RCH 2COOH RCH 2CO 2 HOCO 2 HOO NTs- CO 2Pr -

　sourceH -

　sourceNH 2ONHOCH 3OPhI(OAc) 2KOH / CH 3 OHJOC, 1993, 58, 2478.R CONH 2 R CON IPhOAcKOHR N C OR NH COOCH 3CH 3 OHPhI,

　OAcR CON IPhOAcPhI(OAc) 2CONH 2 RCH 2 Hofmann (see below)R CH 2 NHR"4-i. 14-i. 2R CH 2 NHR"RCH 2 COZR CH 2 NH 2RCH 2 COZCONH 2 RCH 2PhI(OAc) 2

　// KOH / CH 3 OHBu 2 AlH

　not use NaN 3

　directly, avoid attack -CLi into structureC(OR) 2C(SR) 2hC-NH 2C-NO 2C NC CC=O C=O 5-agfdcba5-C=C-ORC=C-SRC-OHC=N-OHC=N-HC=SC=OC=Ov.

　via:

　epoxysilaneR COCRR COCH 2 RNaNH 2 NaBH 4 Ac 2 OSOCl 2HNO 2H 3 O +CO 2 H 3 O N 2 H 4OOBr 2 OH -HBrCrO 3NaBH 4OOKOHNaBH 4CeCl 3H 3 O +O 3ZnZnTsNHNH 2MeLi TMSCl MCPBA LAHCrO 3H 2 SO 4CH 2 COR RCH 2 COR RLDA LAHMsClKOtBu HgCl 2aqCH 3 CNPh S S Ph/CH 2 COR RPhCHONHNH 2OH 3 O +N C OCON N NC NHNH 2OH 3 O +HNO 2N 2 H 4SO 2 ClAc 2 ONaBH 4H 3 O +CO 2NaNH 2COOHOAcCOOHCOOHOHOCOOHOi. via:

　-CO 2 Hii. via:

　-haloketoneiii.

　via:

　aldol processiv.

　via:

　thioenol etherR COCH 2 Rcorticosteroidhecogenin acetateCrO 3OO OOHOOOOOHOH OOBrOHOOHBrBr 2NaBH 4OH -HBrZnO OHSiMe 3OCrO 3SiMe 3OHLAHSiMe 3OMCPBASiMe 3TMSClN 2 , Ts -LiMeLiN N TsHLiN N TsMeLiTsNHNH 2N N TsHOdrawback:

　require simple structure, use many powerful agents: MeLi, LAH, MCPBACO2. need Zn, convert to C=O; other choice Me 2 S1. in the presence of CeCl 3 , H- attack C=O; otherwise may attack -C .

　 and give mixture; mechanism: form Ce-H, follow by H -

　transfer

　other choice: use Al(OiPr) 2

　/ iPrOH

　(MPV)H +OOOO HHOPhOPhOHPhPhOKOHPhCHOOH -NaBH 4CeCl 3O 3ZnCOCOOO CeClHCH 3 CN (aq)HgCl 2O OSPhSPhOMsHSPhOLDAPhSSPhLAHMsClKOtBuSPhHthioenol etherlimit for: 6 ring, with 1 -position blockedcamphorepicamphoreijC-BrkC-HOBr

　ii. MCPBAi. hydrolysis5-b C=S C=OCH 3 OOHHS NMe 2NMe 2 OHOHCH 3 OMCPBA5-c C=N-Z C=OC=N-OHC=N-Hi.

　RaNiii.

　TiCl 3iii. KMnO 4 / Al 2 O 3H 3 O +N OHRaNiNH OC NHH 3 O + NH 2OHHO5-d C=OC CHg 2+

　/ H 2 Onot certain of which mechanismH 2 OOHHOOHgXH 2 OHg 2+HgXOHHgJOC, 1972, 37, 2138.JOC, 1970, 35, 858.HgSO 4

　/ H 2 O / H 2 O5-c.15-c.2C(CH 3 ) 3NOHC(CH 3 ) 3OKMnO 4 / Al 2 O 3acetonert, 5 minTHL, 2001, 42, 4775.

　1. DIBAL / H 3 O +CPhNCPhHOCPhN AlH 3 O +Al (iBu) 2 H5-e C=OC NStenphen

　reduction mostly for Ar C N Ar COH J.Org.Syn, 1925, 3, 1874.2. HCl./ SnCl 2

　/

　Et 2 O5-e.1R - CH 2 - CN5-e.25-e.3R - CH 2 - COHR - CH - COHR"R - CH - COR"R"JOC, 1973, 38, 2129.R CH 2 C NHO NRH R" Xn-BuLiO NR R"HCH 3 IO NR R"R""O NR R"R""MgBrRH R"OR""O RR"H 3 O +H 3 O +RHOH 3 O +R" X / n-BuLiCH 3 IR""MgBrH 3 O +OH OH3. OH OHH 3 O +O NR R"HOH OH

　C=OC=C-X5-fH 3 O +Hg 2+

　/ CH 3 CN (aq)C=C-ORC=C-SRreactivity: ORSR>>ORORORSRSRSR>>>>enol etherthioenol etherenaminevinyl chlorideOCH 3OH 3 O +SCH 3OHg 2+CH 3 CN (aq)ORSRNRClXH +- CH 3 OHH 2 OOCH 3+OOHCH 3 OOCH 3ROHORROHOR ROH OH HORtpye:use:OH 3 O +Hg 2+CH 3 CNH 3 O +OOOSSORORRRSSSRSROOORORORORHRC=OC(OR) 25-gOROHHROROHRRacetal ketal hemiacetal hemiketalHg 2 +

　/ H 3 O +H 3 O +

　/ solv (aq)H 3 O +

　/ solv (aq)Hg 2 +

　/ H 3 O +CH 3 OHacid catOOCH 3 CH 3 OO OHOCH 2 CH 2 OHacid catOROROHOHH 3 O +

　/ solv (aq)acid catalystTsOHCSA

　(camphorsulfonic acid)Amberlite resinpreparation:

　acid catalystunstable: only in aqueous acidbasic solution:

　LDA, NaOMeRED:

　LiAlH 4 , NaBH 4organoMetal:

　RMgX, RListable in: a very common protecting group, deprotect back to ketoneType:H C OEtOEtOEtRMgX / H 3 O +H C OEtOEtOEtRMgXR CHOvia:H COEtOEtRMgXR COEtOEtHR CHO

　NH +2Cr 2 O 7 - 2NHCl.CrO 3+ Et 3 NHCl+ Cl, CO, CO 2+ HOAcH 3 C S CH 3OCOCH 3OHOHDMSOR C ROHR C RODMSOEt 3 NOAc 2 OH 3 C S CH 3OCOCOOHOCRHR+ Me 2 S+ Me2 SAg 2 O:1. a mild oxidizing agent2. must be freshly prepared:

　NaOH into AgNO 3

　(aq)3. may involve surface change, react with CO 2 , lightSwern oxidation:

　(DMSO, oxalyl chloride, Et 3 N)drawback: react at low TCollins reagent: (CrO 3

　- 2 Py)1. drawback: use 6 equivalent, a messy reaction2. must be very dry, fire easily; purify by CaH 23. an old oxidizing material, isolated by Collin. Ag 2 Oi. Jones reagentii. KMnO 4i.

　 PCCii.

　PDCiii. Jones reagent

　(Na 2 Cr 2 O 7 -H 2 SO 4

　/ acetone)iv. Moffatt oxidation

　(DMSO / Ac 2 O)v.

　Swern oxidationvi. DDQ / dioxanevii.

　MnO 2

　/ CHCl 3viii.

　Oppenauer zoidation

　Al(OiPr) 3 ,

　acetoneix.

　K 2 Cr 2 O 7

　(s), rtR C OHOaldehyde1 st

　 alcohol2 nd

　alcohol1 st

　alcoholR C OHOR C ROR C HOC=OC-OH 5-hi.

　 PCCii.

　PDC iii. Collins reagent CrO 3

　- 2 Pyiv.

　N-oxide

　v.

　DMSO / DCCvi. DMSO / HClvii. DMSO / NHCO 3

　/ NaIviii.

　Dess-Martin ReagentJOC, 1985, 50, 1332. NOCH 3OHRCH 2 OHR C HO+NOCH 3O+ClCO-CO 2 HSwern oxidationMoffatt oxidationJOC, 1997, 62, 5246.Al(OiPr) 3HOOacetoneSynthesis, 1979, 537.JOC, 1980, 45, 1596.DDQ:OHMeOHOOMeOHODDQdioxaneNOCH 3O +OOCN ClCl CNPDC (pyridinium dichormate)

　 (H 2 Cr 2 O 7

　+ 2 Py) TH, 1978, 2771.THL, 2002, 43, 8843.PCC (pyridinium chlorochromate)

　(Py-HCl-CrO 3 )TH, 1975, 2647.

　most widely useduse 1 - 1.2 eq.solvent freePfitzner-Moffatt oxidationSSOHSSOHDMSODCCCan. J. Chem, 1978, 56, 1268.PhCH 2 OH PhCHODMSOHClSynLett, 2002, 2041.PhCH 2DMSOPhCHHO SCH 3CH 3via:OOPhBrDMSOOOPhOH NaHCO 3

　/ NaI60 %Synth. Commun., 1986, 16, 1343.70 %92 %PDCH 11 C 5 CHO H 11 C 5 CH 2 OHPDCO CHOOOHTHL, 1979, 5, 399.JOC, 1977, 42, 1991.Synthesis, 1981, 165.OIOOAcOAcAcOJACS, 1991, 113, 7277.CH 2 Cl 2 , rt, 30 min

　pH 6: weak acid buffer, avoid interfere with ketal group pH6TiCl 3pH1TiCl 3OO ONO 2O OOONO 2OH 3 O +Et 3 NON OON OOHH 3 O +OPhNHPhMCPBAPhN C PhOH 3 O +PhN C PhHoPhN C PhNPhPhOHNPhPhOOONH 2PhNH 2PhPhPhCHO-

　PhCHOMcMurray reactioni.

　Corey approach:

　subtituted-quinone // H 3 O +ii.

　Watt approach

　 a. PhCHO // MCPBA // H 3 O +

　 b. ArPhO

　//

　MCPBA

　// H 3 O +

　 c.

　NBS

　//

　KOH

　//

　H 3 O +C=O C-NX 2 5-iONO 2PhOPhPhOPhNH 2PhPhNH 2NCOH// H 3 O +OOOPhPh5-i. 15-i. 2C=OC-NH 2C=OC-NO 2i. Et 3 N

　// H 3 O +Nef reactionii. TiCl 3

　/ pH 1 or 6iii.

　SiO 2

　/ NaOH // H 3 O +JACS, 1977, 99, 3861.iv. LDA / MoO 5 -Py -

　/ HMPT // H 3 O +v.

　NaOH // CH 3 OH / H 2 SO 4

　// H 3 O +THL, 1981,

　5235.Synthesis, 1988, 379.SNO 2PhSOMePhOMeSOPh1. NaOH2.CH 3 OH

　H 2 SO 4H 3 O +PhCHOMCPBAOOH 3 O +vi.

　KMnO 4

　/ KOH JOC, 1969, 34, 2438.ONOMnOOOOONOMnOOOO - MnO 2 - NO 3 -O NO 2KOHNO -O -KMnO 4Chem. Rev. 1955, 55, 137.

　C=OC-Br 5-jC=O C-H 5-kIOOOHO(3 eq.)JACS, 2001, 123, 3183.CH 3CHO2. DDQ / TFA.Synthesis, 1979, 537.NHCH 3 ArDDQNCH 2 ArTFANHArO CF 3ONArOOCF 3DDQNHCHO ArH 3 O +PhCH 3O SeO 2SePhOHOJCS, 1932, 1875.Ph-F / DMSO3.1. SeO 2a select oxidantindrect: change to RC-OH followed by oxidationdirect:1. DMAPO / DBU / CH 3 CNi. DMSO / AgBF 4RBrROSH-

　AgBrDMSO / AgBF 4- Me 2 SPhHNNMe 2ONNMe 2ODMAPON,N-Dimethylaminopyridineoxidevia:Bull Soc. Jpn., 1981, 54, 2221.THL, 1974, 917.2. NaIO 4

　/ DMFTHL, 2003, 44, 1375. OBr84 %150 o C, 40 minNaIO 4

　/ DMFa new method3. DMSO reagents:ii. DMSO / ZnSRCHBrMe RC(O)MeDMSOBrOHOOHZnSDMSOJACS, 2003, 68, 2480.ROAgBF 4

　THL, 1975, 4467.-HOAcRCHOn-BuLiKOtBuAc 2 OR C C R"R CSO 2 PhC R"HR CSO 2 PhC R"OAcR CSO 2 PhC R"OHR CH 2 SO 2 PhC C R CHOHRR C C HC C R R" R C C HR C C Ar R C C H-+C C R PhC C R PhR C C HIIPdPd C C RPhPd IPhPh-IIIn-BuLiR C C HPdR C C LiOMeC C ROCH 3NHClOMeR COHR C C COHHRR C C Lin-BuLiR C C HLiBrR BrRLiHsteric base, prevent Nu attackn-BuLi:

　not MeLi, or t-BuLi, fire easilyRX:

　R-Br, R-TOS, RCHO, RC(O)R n-BuLi / R"CHO // Ac 2 O // KOtBuClOMeNLiiii. ii.

　(Ph 3 P) 2 PdCl 2 , CuI, Et 2 NH / PhIi.

　n-BuLi / RXRCH 2 -SO 2 Ph RC CR" 6-bRC CR"RC CH6- abcdeg6-aC CC CC C- PhSO 2 Hsulfonic acid:

　PhSO 3 H;

　sulfinic acid: PhSO 2 H;

　sulfenic acid:

　PhSOHaddition

　stericsulfoneiv.

　CuI, NaI, Na 2 CO 3 , R C C CH 2 ClR C C HCl CH 2 C C R"R C C CH 2 C C R"Synthesis, 2000, 691.RCH 2 -SO 2 PhRC CHhfiRCH(CO 2 H)-CH 3-C(O)-CH 3OOOXCRR"=CHX

　in fact:

　convert to C=C firstlyinvolved:

　reduction NaBH 4 , oxidation CrO 3 .Py,

　prevent -H attacked by Br 22.KOtBu1.NaBH 4HOClO HO1.Br 2 /CCl 42.KOtBu3.CrO 3 .2PyPb(OAc) 4LiClCO 2 HO- CO 2 ,- Pb (OAc) 2 , -OAc -Cl -ClCH 3 C RKOtBuBr 2 /CCl 4KOtBuPb(OAc) 4 , LiCl CH CH 2 RCH CH 3 RCO 2 HR CCH 3COO PbOAcOAcOAcC C R HCH CH 3 RCO 2 Hii.

　protect - deprotecti. move to terminalC C C C 6-cNH 2 NHKuse:

　KAPAuse:

　Co (CO) 8

　 //

　Fe(NO 3 ) 3 , EtOHC HRH HRKAPAK + N - HRR C C CHCH 2 CH 2 -CH 2 CH 2 CH 3R C C C C CH 2 CH 2 CH 3HHR C C C C CH 2 C CHR C C C C CH 2 C CHOC CHHOHHOC CHHOCo CoCOCOCOCOCOCOHHOC CHOCo 2 (CO) 8Kirreversible at the final steplimit:

　continueous CH 2 , not branch1.B 2 H 62.HOAcCo CoCOCOCOCOCOCOHHOC CHOFe(NO 3 ) 3EtOHJACS, 1975, 97, 891.C C C C 6-duse: i. Br 2

　/ CCl 4

　 // KOtBu6-euse: Pb(OAc) 4 , LiCl

　//

　KOtBu

　//

　Br 2 /CCl 4

　 // KOtBuC C R HpropargylicalleneFe(NO 3 ) 3 :

　weak oxidizing agentchoose B 2 H 6 , not H 2 /cat:

　Co poison catii. Br 2

　// KOHJACS, 1941, 63, 1180.PhPhPh Ph

　C CH 3 RO6-fi. NaBH 4 , H 3 O + , Br 2 , KOtBuC C R Hii.

　NH 2 OH, NaNO 2

　/ H 2 SO 4

　 //

　Ac 2 O / DMAPiii.

　LDA, ClPO(OEt) 2R C CH 3ONaBH 4R C CH 3OHH 3 O +R C CH 2Br 2R C CH 3OR C CH 3OR C CHR C CHNH 2 OHNaNO 2Ac 2 OH 2 SO 4LDAR C N OHCH 3R C N OH 2CH 3R C N NOOCHHHR C NCNOAcOHHR C CHHOPO(OEt) 2ONNOKOtBuRCHBrCH 2 BrDMAPClPO(OEt) 2LDADMAP:

　4-N,N-Dimethylaminopyridinemixture of Ac 2 O / DMAP: NNCCH 3OR C CH6-guse:

　TsNHNH 2

　/ EtOH, heatOOTHL, 1967, 3943.JOC, 1980, 45, 2526.JOC, 1979, 44, 4116.OOONNHTsTsNHNH 2ONNTsN 2OTs -OH OH 2 O 2Na / NH 3 (l)O(MVK)CH 3OCH CH 2Robinson AnnulationGerman invention, as acylating agentvinyl phosphateLDA:

　Li N(iPr) 2 , ignored a long time, re-introduced by Michigan State U.

　 became famous, appeared every weekO

　HORLiNH 2

　/ NH 3

　(l)RXuse:

　LiNH 2

　/ NH 3

　(l) / R-XOClOCl6-h6-i.RC CR"XR C C R"JACS, 1958, 80, 4599.JACS, 1955, 77, 3293.MePh HOSO 2 CF 3BuLiMe C C Phvia:MeCPhJOC, 1978, 43, 364.ArAr" HBrAr C C Ar"NaOEtvia:ArAr"Bri.

　NaOEt (when X = Br)ii.

　BuLi

　(when X = -OSO 2 CF 3 )?HOR

　heatMCPBARCH=CH 2:PBu 3RCH 2 CH 2 -O-PBu 3RCH 2 CH 2 -OHPh-Se-PBu 3Ph-Se-CNmechanism:heatMCPBAOAcCO 2 MeOAcMeOMeO 2 CNO 2Se NOAcCO 2 MeOAcMeOOHMeO 2 CheatH 2 O 2NMe 2H ONMe 2HCO 2 HHCHOheatAg 2 OCH 3 I

　(excess)NMe 3HOH - I -NH 2NMe 3compare:H 2 SO 4DBNIOHHON Nheatiii. CH 3 Ii. n-BuLiii. CS 2OHO SMeSsyn eliminationheatO CH 3OHRONaor

　KOtBuMsClMsO+minor majorp-TSOHOHapplied for reactions: without rearrangement;

　 no regiosiomerC CH OHDean-Stark(CO 2 H) 2

　/ benzeneOHPhPhOOClClClClOClClNCNCOPd-Ciii.

　Pd-C;

　or

　Ni;

　Pt,

　Rhii. chloronaili.

　DDQuse base:

　DBNi.

　CH 3 I / Ag 2...