重要经典化学反应及其机理

AromalicRoaclions-Condonsalion-Cyclization-EpoxideTransformation-Olof'inalionOxidation

-Roduclion-Rearrangement

RifcetoaEnolate

(=0日,R

R>CO2Li,

OMRs

AldolR?JR3尸。

Ikylation

R2R3

R4Ugi1

OTMSO^OH

MukaiyamaNH2R产H

HN-R

Lewisacid02

「2

Baylis-Hillman人R3HN

QEWGK2

PassieriniRZ0

DABCO

OCondensationRIO

HO呼chaelAdditionO乂R

氏3

Obase

JMO2

Intramolecular

R2’

0RClaisen

Ph

Ri

Ol

Ri

o

R

R

2eCompoundcomROH

Ri

CondensationR

OlefinationRamberg-Backlund>Paquette

BtOHKatritzkyesterolefinationR

RTiCh，ZnCuBase

Bt:benzotriazoleOAc

R—%Julia-Lythgoe

AC'O

orReich-KriefoSOPhBase

CHve-Reich-Sharpless2

wCorey-Winter-Eastwood

1)BrSePh2)NalO

4CICSCI.thenP(OMe)\=/

60HOOH3

/Peterson/=\Chugaev

OHR&

-a-CS.NaOH/Mel

2o

RRiJCope*Mamloc-Wolfenstein

RiEliminationH2O2,then130°Co

CouplingReductive

Homer-Wadsworth-Emmons

CHOWharton

R(EtO)POCHCOR

221NHNH/KOAC

22o

Still-GennariZ-Olefinsynthesis

CHONTsBamford-Stevens-Shapiro

R(EtO)2PoeH2COR1KHMDSHkJ

Ri

Wittig

CHO1

R

Ph3PCH2BrR1

0

彳Tebbe-Grubbs-Petasis

R

后

McMurrycoupling

0Nysted-Takai

乂

R

RtR2CHBr2,Zn,T1CI4eCompound.Com

OlefinationSuzuki,Heck,Stilleetc.

。2侬(。附2Spengler-PfannenstielsugaroxidationDDQHookerquinolineoxidation

02^1(01Pr)4Schenckallyllicoxidation

NBS.NCS,NBP.NBA

O2/CU2CI2Kametaniamineoxidationtonitriles

OppenauerAI[OCH(Me)2]3

H2O2Cope-MamlocN-oxidation

Prilezhaev(doublebondepoxidation)Swem[DMS0-(C0CI)2]

Rubottom(a-hydroxylationofketone)’OxidationMoffatt-Pfitzner(DMSO-DCC)

Baeyer-Villiger(makingester,acid,alcholfromketone)Corey-Kim(DMS-NCS)

0

Jacobsenepoxidation1XKomblum.

BuO2HA/O(acac)2a

SharplessepoxidationR-/DMSO/TEA

H2O2/Urea

Shiepoxidation

RCO3HOxygen,Dess-MartinandIBXNicolaouoxidation

CriegeeozonolysisOzone,Organic

OxaneOxidantsNitroxide

K2s2O8[Boyland-SimsH2sO5PeroxidesDavisOxidationreagent

7IElbsoxidationDMDO

tBuO2H/Ti(OiPr)4Kagan-Modenaoxidation

InorganiceC

Oxidants

ReilySeO2

CriegeereagentPd(OAc)4

OsO4A%。K3Fe(CN)6

CANCe(NH)2(NO)Treibsallyllicoxidation(F3CCOO)2Hg

436CrOj/A%。

KaCrOdNazCrOqCQ3NaCIO3/V2O5

Sarettreagent(CrOypyridine)NaCIO,KOCILiebenHypohalideOxidation

Cornforthreagent(CrO3/HO/pyridine)

2HIO4Adlerphenoloxidation

Collinsreagent(CrOypyridine/CHCl2)

2HNO3/V2O5

JonesreagentUCh/HzSO/AcetoneTPAP(Pr4NRuO4)/NMOLey-Griffithoxidationreagent

HN03

Wacker-Tsujiolefinoxidation(Pd2*)

Brownoxidation(R4N)2CrO7

Pyridiniumchlorochromate(PCC.Corey*reagent)KMnO4

PDCCrO2CI2MnC>2

TeuberQuinonesynthesis(KSOskNODjerassi-RylanderoxidationRuO/NaQ

TrahanovskyetheroxidationCe(NH4)2(NO3)6KonakaNickelodidationagentNiSO4/NaOCI

KennedyoxidativecyclizationR/O7David-Mukaiyama-Uenoselectivedioloxidation(Bu3Sn)O/Br2

Oxidation2

0Amdt-Eisterto

RAlder(Ene)OH

“flQ乂CR、NeberRd

KClO

H°CH2N2R人

baseNH2

Retroene

O2

0Rearrangement以。Smiles

Claisen"ph

#phSommelebHauser

basePh

OdCopePh

SigmatropicCationotropicStevens

_'N+

0o。。base

CarrollPh

HO

Wittig

、nS1eCompound.Combase

MeisenheimerN，OX0Wolff

FI

RR,NaN3Ri

Wittig[2,3]sigmatropicrearrangementofallyletherAnionotropicE°HWagner-Meerwein

Pinacol

Demjanov

OHOHH+

Benzilicacid、oO

oc,Favorskii

NaOHOHOHR

HO

NBeckmannr0

AOH।Brook

RICurtiusc人：

RHSORI*NHC、'NSi

24base

R人Ot

SchmidtR

人HOPummerer

RYN-OR

NaN31R

AqO

o

WHTiemannAc

Mislow-Evens

R乂*嗔

TsCl

Rearrangement%

GroupIIIHydride-DonorGroupIVHydride-DonorMetals

LAHL1AIH4BirchreductionNa/NH3

Kursanov-PamesreactionEt3SiH/TFA

ChanreductionofacetyleneBouveaultreductionNa/EtOH

LIAIH(OCHCHOCH)2Chatgilialoglureducingagent

2223ClemmensenreductionZn/Hg

)Tris(trimethylsilyl)sjlaneTTMSS

LiAIH[OC(Me)33Fe/HCl.Zn/H*.ZnfOH

LucheCereducingagentNaBH/CeCl3Meerwein-Ponndorfreduction

4Others

NaBHMcFadyen-StevensesterreductionNHNH

4Reduction22

Na(OAc)3BHWotff-Kishner-HuangMinionreductionNH2NH2

NaBHjCNBorchreductionEschweiler-ClarkreactionHCOOH

BH3CBSreductionMidlandreduction

OhshiroBromoalkenereductionHPO(OEt)2

AIH3

StaudingerAzidereductionPPh

((Me)2CH(Me)CH]2BH3

DIBAL[(CH3)2cHeHzkAIHNa2s2,(NH4)2S.NaS2O4.Na2SO3

Catalysts:ChiralHydrogenation:

Adam'scatalystPtO2

LindarPd(BaSO4)

Noyori'scatalysts.Ruthenium

PearlmanPd(OH)2

RaneyNi(W1〜Wa)

Wlkinson'sRhCI(Ph3P)3

Pd/C.Cu(CrO2)2

Hydrogenresouse:SolviasJosiphos

Hydrogengas

Transferhydrogenation■0,AeC

(diimide.NHNH.NHCOH)Bn

Reduction224difficultR

RingFormation

Arene-OlefinphotoadditionRobinsonannulation

(Nucleophilicaddition,photaddition)

Dieckmannconciensation

Diels-AlderreactionIntramolecularaldolcondensation

1,3-DipolarcycloadditionIntramolecularMichaelreaction

[2+2JCycloadditionIntramolecularNucleophilicalkylation

(ketene,photochemical.Patemo-Buchi)Cyclopentenoneannulation

(alkylation.Wacker,condensation)

[2+3]Cycloaddition

Anioniccyclization

Divinylcyclopropanerearrangement

Electrocyclicreactions

IntramolecularEnereactioneC

Oxy-Enereaction,Comareaction

1,3-SigmatropicrearrangementPauson-Khandreaction[2*2+1],Cc>2(CO)6

(vinylcyclobutane,vinylcyclopropane.

carbonyl/iminecyclopropane)Carbonylaboncyclization,Pd

CyclopropenoneketalcycloadditionOlefinringdosingmetathesis.Mo.Ru

([2+1],[3+21，4+3].[4+2])

NazarovCation-Olefincyclization

Freeradicalcyclization

[reductivecouplingofcarboxylate(acyloin,Ruhlmann)J

[reductivecouplingofketoneoraldehyde(pinacolcoupling.McMurry)]

[Sml2.Bu3SnH.BzOOBz]

Carbenecycloaddition

(halocartoene,Simmons-Smithreaction

diazocartoeneaddition,metal-carbene)

Birchreduction

Cyclization

Aromatic

Reactions

top

Electrophilicsubstitutiononphenylring

Nudeophilsubstitutiononphenylring

EWG:electronicwithdrawgroups.

Diazotizationrelatedreactions.

NHz

NaNO2/HX

orRONO

H

CommonTransformationofEpoxidetop

〃…arecentmemoirbyaHerrvan'tHoffon"theArrangementsofAtomsinSpace,“adocumentcrammedto

thehiltwiththeoutpouringsofachildishfantasy...ThisDr.J.H.van'tHoff...notasteforaccurate

chemicalresearch...ByH.Kolbe(oneofthemosteminentorganicchemistofthetime).10yearslater

van'tHoffwasnamedthefirstrecipientoftheNobelPrizeinChemistry.

A

AcetoaceticEsterSynthesisisaveryusefulbasicreactioninetherindustryoracademia.Themethylene

groupinacetoacticestercouldbeeasilyalkylated,anddoublealkylatedunderbasiccondition.One

conditionIusedfrequentlyisacetoneassolvent,K2c6asbase,andalkylbromideasalkylationreagent.

Thereactionrarelyletsmedown.

Simonsen,J.L.;Storey,R.J.Chem.Soc.1910,95,2106

Simonsen,J.L.;Storey,R.Proc.Chem.Soc.1910,25,290Clickheretolearnmore.

Alder(Ene)ReactionisthermalorcatalyticsigmatropicrearrangementwithH-trasferandcarbonbond

formation.

eC

Clickheretolearnmore.

AldolcondensationisareactionthatgeneratedlotsofPh.D.inorganicsynthesis.Noneedtotalkabout

it.Thealdolcondensationusingaldehydeandsilylenoletherasstartingmaterials,andlewisacid,like

TiCltascatalystiscalledMukaiyamaaldolcondensation.

Kane,R.Ann.Phys.Chem.Ser.21838,44,475

Kane,R.J.Prakt.Chem.1838,15,129Clickheretolearnmore.

A1gar-F1ynn-OyamadaReactionisthesynthesisofflavonolsviatheintermediatedihydroflavonolsmadeby

oxidationofo-hydroxyphenylstyrylketoneusinghydrogenperoxide.

Clickheretolearnmore.

Allen-Millar-Tnppetrearrangement.

Clickheretolearnmore.

AmadoriRearrangementistheconversionofA^-glycosidesofaldosestoN-glycosidesofthecorresponding

ketones.

THOHOH

汽步N、「H否白型MR

OHOHOH

eC

H

_叫这尸

一叫.

OHOHH

Clickheretolearnmore.

Angeli-Riminihydroxamicacidsynthesis

q/OH____(R/。H_贝,。H

0qPh卜44、PhH

。0eC

Clickheretolearnmore.

AppelHalogenation