-AromaticReactions-Condonsation-Cyclization-EpoxideTransformation-OlefinationOxidation

-Reduction-Rearrangement

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1ClPfTWT^rwBrZnMg

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Cyclization

Aromatic

Reactions

top

El*豺qphll后網(wǎng)glMIgpnph洋哥ring

|T^r褶as吟嗎FH

刖口崢hd

闞*no^ufiU或

M鬧二曲iiwK電怖sianphenylring

EV惘腓抑岫押郎和pg

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,K2cO3asbase,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.

Clickheretolearnmore.

AldolcondensationisareactionthatgeneratedlotsofPh.D.inorganicsynthesis.Noneedtotalkabout

it.Thealdolcondensationusingaldehydeandsilylenoletherasstartingmaterials,andlewisacid,like

TiCl-t,ascatalystiscalledMukaiyamaaldolcondensation.

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

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

Algar-F1ynn-OyamadaReactionisthesynthesisofflavonolsviatheintermediatedihydroflavonolsmadeby

oxidationofo-hydroxyphenylstyrylketoneusinghydrogenperoxide.

Clickheretolearnmore.

Alien-Mi1lar-Trippetrearrangement.

Clickheretolearnmore.

AmadoriRearrangementistheconversionofvWglycosidesofaldosestoN-glycosidesofthecorresponding

ketones.

Clickheretolearnmore.

AsingerThiazolineSynthesis

s-s

Clickheretolearnmore.

Auwersreactionistheexpansionofcoumaronestoflavonols.

K.v.Auwersetal.,Ber.41,4233(1908);48,85(1915);49,809(1916)

K.v.AuwersandP.Pohl,Ann405,243(1914)

Clickheretolearnmore.

Azocoupling

eC

Clickheretolearnmore.

BC

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BaeyerPyridineSynthesis

Clickheretolearnmore.

Baeyer(JohannFriedrichWilhelmAdolf[von]Baeyer1835-1917)-Villiger(VictorVilliger1868-1934)

Oxidationisanoxidativerearrangementreactioninitiatedbynucleophilicattack.Theorderofmigratory

aptitudeis30-alkyl>20-alkyl>benzyl>phenyl>V-alkyl>cyclopropyl>Me>>H.Ifitisusedinphenyl

aldehydetomakephenol,thereactioniscalledDakinoxidation.

Clickheretolearnmore.JohannFriedrichWilhelmAdolfvonBaeyer,NobelPrizeChemistry1905.

Baker(WilsonBakerb.1900)-Venkataramanrearrangementistherearrangementofo-ketoesterofphenol

too-hydroxy-1,3-diketone.The1,3-diketonecouldcyclizetoformflavone.

Baylis(A.B.Baylis)-Hillman(M.E.D.Hillman)Reactionistheactivatedvinylsystemtoreactwithketone

oraldehydetoyieldalpha-hydroxylproducts.

eComp0L

Liebig,J.Ann.Chem.1838,25,27

Zinin,N.Ann.Chem.1839,31,329Clickheretolearnmore.

BenzoinCondensationiscyanide-catalyzedcondensationofaromaticaldehydestogivebenzoins.

eC

Lapworth,A.J.J.Chem.Soc.1903,83,995

Lapworth,A.J.J.Chem.Soc.1904,85,1206Clickheretolearnmore.

Bergman(RobertGeorgeBergman)Cyclizationisthecyclizationofenediynestogenerate1,4-benzenoid

diradicals.

Clickheretolearnmore.

BernthsenAcridineSynthesisisthesynthesisof5-substitutedacridinesbydiarylaminesinorganicacids

oranhydrides.

Clickheretolearnmore.

Biginellipyrimidonesynthesisisthe3componentsformationoftetrahydropyrimidinones.

Clickheretolearnmore.

Bischler-Mohlauindolesynthesisistheformationof2-substitutedindolesbyheatingalpah-haloor

hydroxy-ketonewithexcessamountofaniline.Theexcessamountanilineishighlyimportantforthesuccess

ofreactionandmechanism.Thisisaproposedmechanismfromaexperiencedcolleague.

Clickheretolearnmore.

Bischler(AugustBischler1865-?)-Napieralski(BernardNapieralski)Isoquinolinesynthesis.Bischler

一NapieralskireactionissimilartoMorgan-Wallsreaction(Pictet-Hubertreaction).

Clickheretolearnmore.

Blanc-Quelletchloroalkylation

Clickheretolearnmore.

Clickheretolearnmore.

Boekelheidereaction

cB

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Cannizzaro(StanislaoCannizzaro1826-1910)disproportinationreactiontellsthataldehydeisnotvery

stableunderbasiccondition.

Clickheretolearnmore.

Carrollrearrangement

Clickheretolearnmore.

Chapman(ArthurWilliamChapman1898-?)rearrangement

Clickheretolearnmore.

Cook-Heilbronthiazolesynthesis

Clickheretolearnmore.

CopeeliminationreactionisthesjTT-eliminationofN-oxidesoftertiaryamines.Youcancomparethis

reactionwithanotherelimination,Hofmannelimination,inwhichaquaternaryammoniumslatundergoes

eliminationtoformlesssubstitutedolefin.Theleavinghydrogenismoreacidicorlesshindered.Hofmann

eliminationwasusedalotinearlystagealkaloidstructureidentification.

eCompoundoom

Clickheretolearnmore.

Cope(ArthurClayCope1909-1966)Rearrangementistheconversionofa1,5-hexadienederivativebythe

[3,3]-sigmatropicmechanism.Thereactionisbothstereospecificandstereoselective.

eC

Clickheretolearnmore.

Corey(EliasJamesCorey1928-)-Bakshi-ShibataReduction,oxazaborolidine(CBSreagent),isused

toreduceaketoneenantioselectivelybyborane.ThecatalystcanbemadefromL-prolineorD-proline.You

canbuycommerciallyavailablecatalystsfromAldrich.Theenantioselectivityisobtainedbythedifferent

sterichinderancebetweenlargeandsmallgroupsinketone.

Corey,NobelPrizeChemistry1990.

Clickheretolearnmore.

Corey-Chaykovskysulfurylidereaction

Clickheretolearnmore.

Corey-Kim(A.U.Kim)Oxidation

Clickheretolearnmore.

Corey-Linkreaction

Clickheretolearnmore.

Corey-Seebachreaction

Clickheretolearnmore.

Corey-Winter(RolandArthurEdwinWinter1935-)olefinationisthesynthesisofalkenesfromvicinal

diols.Thismethodhasbeenparticularlyusefulinsynthesizingsubstrateswithdelicatestructurefeatures

suchasstrainedandtwistedolefins,unsaturatedcarbohydrates,macrocycliclactones,aswellasin

establishingthestero-chemistryofdiolfunctionsinnaturalproducts.

Clickheretolearnmore.

Cornforth(JohnWarcupCornforth1917-)oxazolerearrangement

Clickheretolearnmore.Cornforth,NobelPrizeChemistry1975

Criegee(RudolfCriegee1902-1975)ozonolysisisaverycleanreaction.Criegeeglycoloxidationisthe

oxidationof1,2-glycoltotwocarbonylbyleadtetraacetate(LTA).

Clickheretolearnmore.

Curtius(TheodorCurtius1857-1928)rearrangement

Clickheretolearnmore.

BC

I)

Dakin-Westreaction

Danshiefsky(SamuelJ.Danishefsky1936-)diene

Darzens(GeorgeDarzens1867-1954)reactionisaalphahaloestertoreactwithaketoneoraldyhydegive

aglycidicesterwithanepoxidering.

DavisOxidizingreagentisthecamphory1sulfony1oxaziridinederivativeusedtodoenatio-selectively

alpha-hydroxylationofcarbonylcompounds.ComparewithOppoIzerchiralauxiliary.

Davidsonoxazolesynthesis

deKimpeamidinesynthesis

DeMayocycloadditionisthesynthesisof1,5-diketones.

Delepine(StephaneMarcelDelepinel871-1965)Aminesyntheisis

Ph6吟

B廠

Demjanov(NikolaiJakovlevichDemjanov1861-1938)rearrangementisacarboncationrearrangementgenerated

byanamineandnitrousacid.Thisreactionappearstobeusefultopreparationoffive,six,andseven

memberedrings,andtobelessvaluableforthepreparationofsmallerorlargerrings.

N-QHN￡0打小

/一＞血—＞乩

一"一Q/_(5

Dess(D.B.Dess)-Martin(JamesCullenMartin1928一)Oxidationreagentisaperiodinanereagenttooxidize

thealcoholtoaldehydeorketone.Theredintermediateisveryeasytodecompose,explosionisapotential

hazard.ThesametypeofoxidationreagentisIBX.

o

Dieckmann(WalterDieckmann1869-1925)(Claisen)estercondensationisthesythesisofopenorcyclic

beta-ketoesters.Thisreactionissimilartobase-catalyzedAldolcondensation.

Diels(OttoPaulHermannDiels1876-1954)-Alder(KurtAlder,July10,1902-June20,1958)cycloaddition

isoneofmoststudiedreactions,andhugenumberoforganicchemistryPh.D.saregeneratedfromthis

reaction.Noneedtotalkanymore.

DielsandKurtAlder,NobelPrizeChemistry1950.

Dimrothtriazolesynthesis

Molecules2001,6,574-587

Dornow-Wiehlerisoxazolesynthesis

EFGHK

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Eschenmosercouplingreactionthesynthesisofenaminoketonesfromthioamidesorbeta-dicarbonyl

derivativesfromthioesters.

Ferrario-Akermannthiocyclization

Finegantetrazolesynthesis

RN

Finkelstein(HansFinkelstein1885-1938)reaction

J

Fisher(EmilHermannFischer1852-1919)indolesynthesis

Forsterdiazosynthesis

Forster-Deckeraminesynthesis

Freidel(CharleFriedel1832-1899)-Crafts(JamesMasonCrafts1839-1917)reaction

Friedlander(PaulFriedlander1857-1923)quinolinesynthesis

Fujimoto-Be11eaucyclohexenone

GEFHIJK

GiIman-vanEssketonesynthesis

eCowaEew苜

Gomberg(MosesGomberg1866-1947)-Bachmann(WernerEmmanuelBachmann1901-1951)reaction

Graham(WilliamHardinGraham1932-)diazirinesynthesis

GranacherHomologation

Haller-Bauerketonecleavage

臭-PgrpPh—PhY

對(duì)彳、Ph一M曬

Hantzschthioazolesynthesis

HH

RCoR送R、

Ry。HN寸

cr

Hantzsch(ArthurRudolfHantzsch1857-1935)pyridinesynthesisisanonepotreactiontomakepyridine

fromabeta-ketoester,aaldehyde,andammonia.

R

l0R

HgCOOC.-GOOCH3FrJyCOQCHs

X

K一噂一3二

r

叫H

FWR