Synthesis of Heterocycles via Metal-Catalyzed Reactions that Generate One or More Carbon-Heteroatom Bonds

276 Pages·2013·8 MB·English

by  John P. Wolfe (auth.)

Topics in Heterocyclic Chemistry 32
Series Editor: B.U.W. Maes, Janine Cossy and Slovenko Polanc
John P. Wolfe Editor
Synthesis of
Heterocycles via
Metal-Catalyzed
Reactions that
Generate One or
More Carbon-
Heteroatom Bonds
32
Topics in Heterocyclic Chemistry
Series Editors:
Bert U.W. Maes, Antwerp, Belgium
Janine Cossy, Paris, France
Slovenko Polanc, Ljubljana, Slovenia
Editorial Board:
D. Enders, Aachen, Germany
S.V. Ley, Cambridge, UK
G. Mehta, Bangalore, India
K.C. Nicolaou, La Jolla, CA, USA
R. Noyori, Hirosawa, Japan
L.E. Overmann, Irvine, CA, USA
A. Padwa, Atlanta, GA, USA
For furthervolumes:
http://www.springer.com/series/7081
Aims and Scope
The series Topics in Heterocyclic Chemistry presents critical reviews on present
andfuturetrendsintheresearchofheterocycliccompounds.Overallthescopeisto
covertopicsdealingwithallareaswithinheterocyclicchemistry,bothexperimental
andtheoretical,ofinteresttothegeneralheterocyclicchemistrycommunity.
The series consists of topic related volumes edited by renowned editors with
contributionsofexpertsinthefield.
John P. Wolfe
Editor
Synthesis of Heterocycles via
Metal-Catalyzed Reactions
that Generate One or More
Carbon-Heteroatom Bonds
With contributions by
A. Aponick (cid:129) N.A. Butt (cid:129) S.R. Chemler (cid:129) D.A. Copeland (cid:129)
L.D. Julian (cid:129) J. Keilitz (cid:129) J.M. Ketcham (cid:129) M. Lautens (cid:129)
H.A. Malik (cid:129) J. Waser (cid:129) J.P. Wolfe (cid:129) W. Zhang
Editor
JohnP.Wolfe
DepartmentofChemistry
UniversityofMichigan
Michigan
USA
ISSN1861-9282 ISSN1861-9290(electronic)
ISBN978-3-642-38879-8 ISBN978-3-642-38880-4(eBook)
DOI10.1007/978-3-642-38880-4
SpringerHeidelbergNewYorkDordrechtLondon
LibraryofCongressControlNumber:2013943916
#Springer-VerlagBerlinHeidelberg2013
Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionor
informationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar
methodologynowknownorhereafterdeveloped.Exemptedfromthislegalreservationarebriefexcerpts
inconnectionwithreviewsorscholarlyanalysisormaterialsuppliedspecificallyforthepurposeofbeing
enteredandexecutedonacomputersystem,forexclusiveusebythepurchaserofthework.Duplication
ofthispublicationorpartsthereofispermittedonlyundertheprovisionsoftheCopyrightLawofthe
Publisher’s location, in its current version, and permission for use must always be obtained from
Springer.PermissionsforusemaybeobtainedthroughRightsLinkattheCopyrightClearanceCenter.
ViolationsareliabletoprosecutionundertherespectiveCopyrightLaw.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexempt
fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse.
While the advice and information in this book are believed to be true and accurate at the date of
publication,neithertheauthorsnortheeditorsnorthepublishercanacceptanylegalresponsibilityfor
anyerrorsoromissionsthatmaybemade.Thepublishermakesnowarranty,expressorimplied,with
respecttothematerialcontainedherein.
Printedonacid-freepaper
SpringerispartofSpringerScience+BusinessMedia(www.springer.com)
Preface
ThisvolumeofTopicsinHeterocyclicChemistryisfocusedonnewandinnovative
metal-catalyzedreactionsthateffectformationofacarbon–heteroatombond.The
volumeiscomposedofsevenchapters,whichhavebeenwrittenbyatalentedgroup
ofyoungscientistswhohaveallmadesignificantcontributionstothisfield.
The first five chapters of this volume are centered on the construction of
saturated heterocycles from alkenes bearing appended nitrogen or oxygen
nucleophiles. The first chapter, entitled “Synthesis of Saturated Heterocycles via
Metal-CatalyzedAlkeneCarboaminationorCarboalkoxylationReactions,”whichI
have written, is focused on reactions of these substrates with various carbon
electrophiles. These transformations generate both a carbon–carbon bond and a
carbon–heteroatom bond and provide stereocontrolled access to a broad range of
heterocycles.
Inthesecondchapter,entitled“SynthesisofSaturatedHeterocyclesviaMetal-
CatalyzedAlkeneDiamination,Aminoalkoxylation,orDialkoxylationReactions,”
Chemler and Copeland outline reactions that generate two carbon–heteroatom
bonds.
Inthethirdchapter,entitled“SynthesisofHeterocyclesviaPalladium-Catalyzed
Wacker-TypeOxidativeCyclizationReactionsofHydroxy-andAmino-Alkenes,”
ZhangandButtdescribethesynthesisandhighlighttheprogressthathasbeenmade
inthisfieldinrecentyears.
In the fourth chapter, entitled “Synthesis of Saturated Heterocycles via Metal-
Catalyzed Hydroamination or Hydroalkoxylation Reactions,” Julian provides a
highlycomprehensivelookandincludesaconsiderableamountofusefulinforma-
tionaboutthemechanismofthesetransformations.
In the fifth chapter, entitled “Synthesis of Saturated Heterocycles via Metal-
Catalyzed Allylic Alkylation Reactions,” Aponick and Ketcham outline recent
progressmadeandillustratetheutilityofthesetransformationsfortheconstruction
ofcomplexmolecules.
Thefinaltwochaptersinthisvolumearealsolargelycenteredonthereactivity
of alkenes and alkynes in heterocycle-forming processes, but focus on different
types of substrates as compared to the first five chapters. In the sixth chapter,
v
vi Preface
entitled “Synthesis of Saturated Heterocycles via Metal-Catalyzed Domino/One-
Pot Reactions that Generate a C–N or C–O Bond,” Lautens, Keilitz, and Malik
provideanupdateonrecentdevelopmentsinthesynthesis.
Intheseventhchapter,entitled“SynthesisofSaturatedHeterocyclesviaMetal-
Catalyzed Formal Cycloaddition Reactions that Generate a C–N or C–O Bond,”
Waser rounds out the volume with a new look at the synthesis, which nicely
illustratestheutilityofstrainedmoleculesinheterocyclesynthesis.
Iwouldliketothankallofthecontributingauthorsforprovidinginterestingand
insightful chapters, and I also appreciate the hard work of the staff at Springer
(especiallyAnetteLindqvistandTanjaJaeger).Finally,Iamparticularlygratefulto
serieseditorBertMaesfortheopportunitytoorganizethisvolume.
AnnArbor,MI JohnP.Wolfe
Contents
SynthesisofSaturatedHeterocyclesviaMetal-CatalyzedAlkene
CarboaminationorCarboalkoxylationReactions. . . . . . . . . . . . . . . . . 1
JohnP.Wolfe
SynthesisofSaturatedHeterocyclesviaMetal-CatalyzedAlkene
Diamination,Aminoalkoxylation,orDialkoxylationReactions. . . . . . . 39
SherryR.ChemlerandDavidA.Copeland
SynthesisofHeterocyclesviaPalladium-CatalyzedWacker-Type
OxidativeCyclizationReactionsofHydroxy-andAmino-Alkenes. . . . . 77
NicholasA.ButtandWanbinZhang
SynthesisofSaturatedHeterocyclesviaMetal-CatalyzedAlkene
HydroaminationorHydroalkoxylationReactions. . . . . . . . . . . . . . . . . 109
LisaD.Julian
SynthesisofSaturatedHeterocyclesviaMetal-CatalyzedAllylic
AlkylationReactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
JohnM.KetchamandAaronAponick
SynthesisofHeterocyclesviaMetal-CatalyzedDomino/One-Pot
ReactionsThatGenerateaC(cid:1)NorC(cid:1)OBond. . . . . . . . . . . . . . . . . . . 187
JulianeKeilitz,HasnainA.Malik,andMarkLautens
SynthesisofSaturatedHeterocyclesviaMetal-CatalyzedFormal
CycloadditionReactionsThatGenerateaC–NorC–OBond. . . . . . . . 225
JeromeWaser
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
vii
TopHeterocyclChem(2013)32:1–38
DOI:10.1007/7081_2012_98
#Springer-VerlagBerlinHeidelberg2013
Publishedonline:28February2013
Synthesis of Saturated Heterocycles via
Metal-Catalyzed Alkene Carboamination
or Carboalkoxylation Reactions
JohnP.Wolfe
Abstract This review describes recent advances over the past decade in the
fieldofheterocyclesynthesisviaPd-catalyzedalkenecarboaminationorcarboalk-
oxylationreactions.Thesetransformationseffectthecouplingofacarbonelectro-
phile with an unsaturated alcohol or amine and provide heterocyclic products via
difunctionalizationofthesubstratealkene.Thesereactionsprovidestereoselective
accesstoabroadarrayofoxygenandnitrogenheterocycles,includingcompounds
thatcontainmorethanoneheteroatom.Thecurrentscopeandlimitationsofthese
transformationsarediscussed,alongwithrelevantmechanisticdetails.
Keywords Alkene difunctionalization (cid:1) Catalysis (cid:1) Copper (cid:1) Cross-coupling (cid:1)
Gold(cid:1)Heterocycles(cid:1)Palladium(cid:1)Stereoselectivesynthesis
Contents
1 Introduction................................................................................... 2
2 Metal-CatalyzedAlkeneCarboalkoxylationReactions..................................... 2
2.1 Metal-CatalyzedAlkeneAlkoxyarylation,Alkoxyalkenylation,and
Alkoxyalknylation...................................................................... 2
2.2 Metal-CatalyzedAlkeneAlkoxycarboalkoxylation,Alkoxyacylation,and
Alkoxycyanation....................................................................... 13
3 Metal-CatalyzedAlkeneCarboaminationReactions........................................ 15
3.1 Metal-CatalyzedAlkeneAminoarylation,Aminoalkenylation,and
Aminoalknylation...................................................................... 15
3.2 Palladium-CatalyzedAlkeneAminocarboalkoxylationandAminocarboamidation 30
4 ConclusionandFutureOutlook.............................................................. 31
References........................................................................................ 31
J.P.Wolfe(*)
DepartmentofChemistry,UniversityofMichigan,930N.UniversityAvenue,
AnnArbor,MI48109-1055,USA
e-mail:[email protected]
2 J.P.Wolfe
1 Introduction
Saturated five-, six-, and seven-membered heterocycles are common subunits
displayed in a broad array of interesting and useful molecules. These types of
compounds are found in biologically active natural products and have historically
been of considerable importance in the development of pharmaceuticals and
agrochemicals. As such, there has been a longstanding interest in the invention of
newstrategiesandtacticsforthesynthesisofsaturatedheterocycles.
Over the past decade considerable efforts have been dedicated towards the
development of new approaches to the construction of saturated heterocycles via
metal-catalyzed alkene carboalkoxylation or carboamination reactions. These
transformations typically involve the coupling of a carbon electrophile (such as
anarylhalide)withanalkenebearingapendantnucleophilicheteroatomfunctional
group(suchasanalcoholoramine).Thereactionseffectdifunctionalizationofthe
alkeneunitwiththeformationofoneC–Cbondandonecarbon-heteroatombond,
along with 1–2 stereocenters. In addition, many alkene substrates that contain
stereocenters are transformed to products with high diastereoselectivity. These
methods are highly convergent and are also generally amenable to the rapid
constructionofanalogsofaparticularcompound,asawidearrayofsuitablecarbon
electrophilescanbereadilyobtainedfromcommercialsources.
This review covers the most significant developments in this field over the
past 10 years and illustrates the broad array of different heterocyclic structures
thatcan beaccessed using these methods. Theprimaryfocus ofthis chapter is on
aryl, alkenyl, and alkynyl-derived electrophiles. However, reactions that employ
COandrelatedelectrophilesarebrieflynoted.
2 Metal-Catalyzed Alkene Carboalkoxylation Reactions
2.1 Metal-CatalyzedAlkeneAlkoxyarylation,Alkoxyalkenylation,
and Alkoxyalknylation
2.1.1 Palladium-CatalyzedReactionsofAlkene-AppendedAlcohols
withHalogenatedCarbonElectrophiles
Palladium-catalyzed carboalkoxylation reactions between γ-hydroxy terminal
alkenes and aryl bromides provide an efficient and stereoselective means for the
generation of substituted tetrahydrofurans. These transformations generate 2,5-cis-
and 2,3-trans-disubstuted products with good to excellent diastereoselectivity
(Scheme 1) [1–3]. The reactions are effective with a number of different primary,
secondary, and tertiary alcohol substrates. Alkenyl bromides can be used as
electrophiles in some instances, although chemical yields are not as high as those