官能团转变反应全图解

有机合成图示图解

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Lemsay第1页2017-4-28

有机合成图示图解

FunctionalGroupInterconversion

C=O

C-HC-ORC-OHC-N

5-aC=O

3-aC-H4-a

1-aC-OH2-aC-OHC-HbC=S

bC-ORbC-N

bC-XbC-(OR)cC=N-OH,C=N-H

2cC-XC-X

cC-NH2cdCC

cC(O)ORdC-NH2

dC-SdC-OHeCN

dC-HeC-OCH2OR

eC=OeC=OfC=C-OR;C=C-SR

eC=CfC-OC(O)R

fC=CfC=C

ggC(OR)2;C(SR)2

gC-CNfC-CNC---OHgC-C(O)Z

hC=OhC-OH

hC-CO2HhCN

iCOiC-NH2;C-NO2

iC-CHO

jC=CjC-Br

jC(O)X

kC-H

CCC=CC-XC-CH3

6-aRCCH7-aCH-CX8-aC-OH9-aC-X

bCH-CH

bRCH2-SO2PhbC-NH2

cCCcCX-CYcC=O

dC=CXdC(O)Z

dCC

eRCH(CO2H)-CH3eC-H

e-C(O)-CH3

f-C(O)-CH3

fC=O

g

gCC

OO

XhCCH

hO

i

iCRR'=CHXC=C

j

C-OH

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有机合成图示图解

C-H

1-aC-OHeC=OiC-CHO

bC-XfC=CjC(O)X

gC-CN

cC-NH2

dC-ShC-CO2H

J.Org.Chem.2000,65,6179

O

1-aC-OHC-H

RCHOSCH

23tosylatetoluenesulfonylchloride(s)~$30/Kg

OO

ORCH2OSCH3mesylatemethanesulfonyychloride(l)~$30/Kg

(1).for1',2'alcohol:CH3SClOO

LiAlH4

ORCHOSCFtriflatepurificationtextbook

RCH2-H23

RCH2OHdrypyridine:fromCaHanddistilled

i.p-TsCl//LiAlH4dryPyO2

PhPh

Ph2SiHCl/InCl3PhPh

ii.PhSiHCl/InClPhPh

23via:H

CHCl2Oindiumtrichloride

rt,3hrH

OHCl2InSiPh2InCl3auniqueLewisacidcatalyst,

JOC,2001,66,7741.Clacceleratedeoxgyenation

SnBu3

(2).for3'alcohol:SS

CHSCH

33OCOPhOCOPh

ClCOPhn-Bu3SnHvia:

i.ClC(S)OPh//n-Bu3SnHCH3OHCH3H

CH3CH3thiocarbonate

(anester)stericOK

ii.EtSiH/Lewisacid

3JOC,2000,65,6179.

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有机合成图示图解

1-bC-XC-H

Brn-Bu3SnHH

Bu3SnH:(l),easytoremove

in-Bu3SnH/AlBNPh3SnH:(s),hardtoremove

(1).freeradicalreductionAIBN

Me3SnH:toovolatile,toxic

iiNaBH4/InCl3/CH3CN

JACS,2002,124,906.radicalreagent

JACS,1972,94,8905.

iLiAlH4

(2).hydridereduction

iiNaBH4JOC,1969,34,3923.THL,1969,3095.hygroscopic,driedself,suggest:buysmallamounteachtime

unstableinacid,formH2gas;stableinweakbase

iiiNaBH3CNNaBH3CN:stableatpH5-6

ivLiBHEt3(superhydride)JOC,1976,41,3064.

BrH

iMg/Et2OH2O

(3).metalreductionNa/NH3;Li/NH3;Na/EtOH(Grignardreagent)

iiZn;Fe;Sn;Mg

Br

H

R

n-BuSnHRn-BuSnHR

NNn-BuSn

CNCN-N2CN

(AIBN)n-BuSnBrn-BuSn

azobisisobutyronitrileradicalinitiator

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有机合成图示图解

1-cC-NH2C-H

ArSO2ClBuLi

RCH2NH2RCH2NHSO2ArRCH2NSO2Ar

p-TsClHinsberg'stest-BuH

BuLiLiAlH4tosylamide

(1).RCH2NH2RCH2-H

SO2Ar

OLiAlH4

RCH2NRCH2-H

SOAr

p-TsClNaHNaHp-TsClCH3SCl2

(2).Ar-NHtosylimide

2Ar-HOweakerC-Nbond

NH2Cl

SO2Ar

ArNNaH

NaNOH3PO2via:ArNNHArNNAr-H

(3).2NH

Ar-NH2Ar-H2-ArSOH

HCl2JOC,2001,66,8293.

-AgO

X2OH-

(4).RCH2NH2RCH2NMe3RCH2NMe3R=CH2R-CH3

C-SradicalmechanismJOC,1985,50,427.

1-dC-HEtO2C

EtO2C

HNNRaneyNickel:Ni-Alalloy,suspension

CH2Ph

(1).RaneyNiHNN

ORaneyNiCH2Phburnfilterpaperifdry

MeOCS

(2).Li/NH32mechanismuncertain,probablyradical

MeO2CH

(3).LiAlH4/CuCl2

JCSPerkinTransI,1973,654.

NaBH4/NiCl2

NaBHEt3/FeCl2(orCoCl2,VCl3)

Chemistry:R-SHR-S-RR2SOR2SO2

R-SS-R

remove:Hg+;Ni

Lemsay第5页2017-4-28

有机合成图示图解

C=O

1-eC-HSH

HSRa(Ni)

SH

H

bestsuitableforarylketone(ArCOR);notgoodforconjugateketoneBF3,CH2Cl2SH

OHOO

preparation:HgCl2intoZnHthioketal

CH

(1).Clemmensenreduction:Zn-Hg/HClacidic613thioketal:inerttoLAH;reactwithRaNi;smellterribleandstaylong;discardshoses

similar:Sn/HCl

SH

(2).thioketal:/BF,CHCl//RaNineutral-

SH322NNH2OHH

OOH-NNHHH

NNH

-N2H4-N2

(3).Wolff-Kishnerreduction:N2H4,OH,heatbasic

ONN

Pd-Cmajorside-product:drawbackofthereaction

PhPh

(4).Pd-C/HCO2NH4:mild,efficientPhPh

HCO2NH4

Synthesis,2001,16,2370.

(5).Tosylhydrazonereduction(Shapiroreaction):H

NNTs

(modifiedWolff-Kishnerreduction):)TsNHNH2//REDHforacyclic,mayC=Csideproduct

H-

O

//H2/PtO2BH

(6).enolderivatives:Tf2O/Nlimit:for-Hcompd.REDchoice:MeLi;NaBH3CN(good)

O

LAH,NaBH4:2groupcompeteatStanfordU.

B2H6:veryflamable,fireifshootoutfromsyringe

O

Et3SiH

(7).Et3SiH/CF3COOHNOPhOO

NO2Ph2

CFSOSCF

CF3COOHHO33

OTfHH

OOH

JOC,1973,38,2675.CCCC2CCH

PtO2

N

PtO+H=Pt

22

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有机合成图示图解

1-fC=CC-C-H

H2H2,PtO2

catalyst:RR

PtO

Pd-C2NTFA,60℃N

PtO2R=NHAc,NH

HOHOHinaceticcondition2

(1).H2/catRh-C;Rh-Al2O3;OHHOH

JOC,2002,67,7890.

RhCl(PPh3)3stereoselcetive:samesideasOH(duetoHbond)

Ni

(2).HN=NH(diimide)

JOC,1993,58,4979.CO2MeCO2Me

(3).B2H6//RCO2H,heatORhCl(PPh3)3O

RhCl(PPh3)3

ObenzeneO

+12hr

(4).n-Bu2SnI/MgBr2-Et2O//H3O

OO

Wilkinson'scatalyst:regioselective,preferisolateddoublebondJACS,1979,101,7020.

solubleinorgsolvent,9Phgroup$50/25g

H

via:H

CH3CO2D

BRN2H2:unstable;generatedinsitufrom"DEAD"(diethylazodicarboxylate)JCS,PT1,1986,546.

RDorfrom:N2H4+H2O2;N2H4+Cu(II)+O2;NH2OH+NH2OSO3

prepareisotope

RR

OH-

EtOCNNCOEtCCRR

22HO2CNNCO2HHNNHR

RCC

HHOR

O-2CO2-N2R

NNHH

syn-addition

OO

I

OEtOEt

OEtn-BuSnI+OEt

2H3Onotradicalmech.

MgBr2-Et2Ovia:O

OOIO

SnH

JOC,2001,66,8690.RSn

HRRR

Lemsay第7页2017-4-28

有机合成图示图解

1-gCCNC-H

CN:~X(pseudohalogen),formKCN,NaCNwithIAelements

notquitesame:notforH-

(1).K/Al2O3JOC,1980,45,3227RCCNcharacteristcs:IR,CMR

K/HMPA

whichis+?toxic?

(2).Na/NH3

HMPA:hexamethylphosphoramide(MeN)P=O

23b.p.~230C

=HMPT:hexamethylphosphorictriamide(Me2N)3P=O

highlytoxic,cancersuspectedagent?

modifiedto:NN

yesforwhitemouse,uncertainforhuman

O

Ph

Ph

CCOHC-HO

1-h2R

Hsolvent

O

(1).particularstructure:-COPhNPh

2PhNPh

-CO2

ORCO

(2).normalstructure:SOCl2//PhSeH//n-Bu3SnH2RH

otherClsources:PCl5;(COCl)2RR

oxalylchloridepyridiniumbetaine

(3).organicelectrochemistry

CO2H

-

eOOO

SOClPhSeHn-BuSnH

RCHCOH23

CO2H2RCH2CClRCH2CSePhRCH2H

(radicalmechanism?)

organoseleniumchemistry

Lemsay第8页2017-4-28

有机合成图示图解

1-iCHOC-H