te03701苯炔综述

苯炔综述

Tetrahedron59(2003)

701–730

Tetrahedronreportnumber629

Theuseofarynesinorganicsynthesis

´le`nePellissier*andMauriceSantelliHe

`seOrganiqueUMRno.6009,Faculte´desSciencesdeSaint-Je´ro me,AvenueEsc.Normandie-Niemen,LaboratoiredeSynthe

13397Marseille,Cedex20,France

Received27November2002

Contents

1.2.3.4.

Introduction

StructureandreactivityGenerationofarynes

Pericyclicreactionsofarynes4.1.Diels–Aldercycloadditions

4.1.1.Withcyclicheterodienes4.1.2.Withacyclicheterodienes

4.1.2.1.Intermolecularcycloadditions4.1.2.2.Intramolecularcycloadditions

4.1.3.Withotherdienes4.2.[2þ2]Cycloadditions4.3.1,3-Dipolarcycloadditions4.4.1,4-Dipolarcycloadditions4.5.Enereactions

Nucleophilicadditionstoarynes

5.1.Additionofnitrogennucleophiles5.2.Additionofcarbonnucleophiles

5.2.1.Lithioacetonitrilederivativesascarbonnucleophiles5.2.2.LithioenolatesascarbonnucleophilesTransitionmetal-catalysedreactionsofarynesConclusions

701701702704704704707707709709711712715715717717718718722723727

5.

6.7.

1.Introduction

Thisreviewisanupdateofarynechemistryandcoverstheliteraturefrom1990–2002sinceearlyworkhasalreadybeenreviewedextensively.1Theprecedingreviewcoveredliteraturefrom1980–1992.1cUnlikeitspredecessor,thisreviewincludesthetransitionmetal-catalysedreactionsof

arynes.Theimportanceofarynesforthesynthesisofnaturalproductsparticularlyalkaloidsiswellillustrated.Theterm‘arynes’willbeusedtoreferbothtoderivativesof1,2-dehydrobenzene(benzyne)andtheirheterocyclicanalogues(heteroarynes).Arynesandheteroarynesarereactiveintermediatesderivedformallybytheremovaloftwoadjacenthydrogenatomsfrom,respectively,anaromaticringoraheterocyclicaromaticring.Prototypicalexamplesareo-benzyneand3,4-didehydropyridine(3,4-pyridyne)asdepictedinFigure1.

2.Structureandreactivity

Figure1.Structuresofbenzyneand3,4-pyridyne.Keywords:reactivityofarynes;naturalproducts.*Correspondingauthor.Fax:þ33-4-91-98-38-65;e-mail:h.pellissier@univ.u-3mrs.fr

In1953,Roberts’experimentsontheconversionofC-labeledchlorobenzenewithpotassiumamidetoanilinegavestrongsupporttotheintermediacyofo-benzyneinthisandrelatedreactions.1bFinally,benzynewastrappedasa

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0040–4020/03/$-seefrontmatterq2003ElsevierScienceLtd.Allrightsreserved.PII:S0040-4020(02)01563-

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