C-H and C-X bond functionalization : transition metal mediation

488 Pages·2013·13.51 MB·English

by  Xavi Ribas

C–H and C–X Bond Functionalization
Transition Metal Mediation
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RSC Catalysis Series
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Professor James J Spivey, Louisiana State University, Baton Rouge, USA
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C–H and C–X Bond
Functionalization
Transition Metal Mediation
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8 Edited by
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3 Xavi Ribas
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0. Institut de Quı´mica Computacional i Cata´lisi (IQCC) &
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81 Dedicated to my daughter Laia, my son Arnau and my wife Brenda.
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F Preface
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1 Metal-mediatedorganic synthesishasrevolutionizedthewayorganic chemists
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oi:1 designtheirretro-syntheticstrategiestopreparenewcompoundsunachievable
g | d only a few years ago. Among those strategies, carbon–carbon and carbon–
or heteroatomcross-couplingreactionsmediatedbypalladiumandcopperemerge
c.
s as the most reliable ones to effect the desired C–X bond functionalizations.
s.r
ub More recently, an unstoppable rush in metal-mediated direct C–H bond
p
p:// functionalizations is occurring, which will probably be the major advance in
htt organic synthesis in the first decades of the 21st century. In both of these
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o synthetic strategies, a profound mechanistic understanding is crucial to design
aded y 2013 newThmisetbaolockatagliyvsetss waintheixmtepnrsoivveedopveerrfvoiremwanocfe.the different metal-catalyzed
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wnl4 M methodologies to achieve the desired C–X and C–H bond functionalizations
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Dn toproduceamyriadofneworganiccompounds,givingaprominentrelevance
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d to the molecular mechanistic aspects of the reactions with special attention to
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s the organometallic species and different metal oxidation states involved. The
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u first two chapters deal with copper-catalyzed C–heteroatom cross coupling
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reactions,theso-calledUllmann-typereactions.Chapter1(Ma)coversthekey
role of the commonly used dinucleating ancillary ligands, whereas Chapter 2
(Casitas) discusses extensively the different mechanistic proposals for these
Cu-catalyzed transformations, nowadays under intense debate.
Chapter 3 (Fairlamb) begins a block about palladium-catalyzed reactions,
starting with the fundamental Pd0/PdII redox steps in C–C cross-coupling
reactions, with special emphasis to the everyday most recognized role of the
heterogeneous pathways due to nanoparticle formation, which competes with
the classical homogeneous proposals. Chapter 4 (Vedernikov) then continues
with an overview of different C–heteroatom bond formation reactions
by reductive elimination involving organopalladium(IV) species, which are
involvedinPdII/PdIVcatalyticcycles.Moreover,Chapter5(Mirica)closesthis
RSCCatalysisSeriesNo.11
C–HandC–XBondFunctionalization:TransitionMetalMediation
EditedbyXaviRibas
rTheRoyalSocietyofChemistry2013
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
vii
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viii Preface
block on Pd-based mechanistic understanding by showing the connections
between the recently discovered mononuclear and dinuclear organop-
alladium(III)speciesandthePdII/PdIVredoxchemistry,inC–C,C–heteroatom
bond formation reactions, as well as in C–H functionalization.
The two following chapters of the book deal with metal-catalyzed defluor-
07 ination and fluorination reactions. Chapter 6 (Love) describes in detail the
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66- ranging mainly between group 7 and group 11 of the periodic table (including
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37 Fe).ThenfollowsChapter7(Gouverneur),whichreportsontheimportanceof
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49 fluorination in pharmaceutical industries and medical diagnosis, covering
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81 aromatic, allylic and alkylic fluorinations catalyzed mainly by Pd, but also by
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9/9 Au, Ni and Pt.
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0 The next four chapters are devoted to the recent inrush of direct C–H
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0. activation and functionalization, mainly mediated by palladium catalysts.
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oi: Chapter 8 (Urriolabeitia) covers many examples of the coordination-directed
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g | metallation strategy to effect C–H functionalization at vicinal positions, with
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c. Pdasthemostprominentmetal,butalsoincludingexampleswithCu,Rhand
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s.r Ru. It is followed by Chapter 9 (Lei), which includes direct arylation of
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p areneswitharylhalidesunderthecatalysisofheavy-metalssuchasRh,Irand
p:// Pd, but also first-row transition metals such as Fe, Co, and Ni. In Chapter 10
htt
n (Su)thepalladium-catalyzeddoubleC–Hactivationprocessesunderoxidative
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aded y 2013 ccoonudpiltiniognssdaesrcerihbiegdhliinghtthedis, bboeoinkginsotmeremhoswofthuesincgulnmoinn-aatciotinvaotefdthareencersosass-
nloMa substrates. The last chapter of this block, Chapter 11 (Liu), is devoted to
Down 24 aerobic oxidative Csp2–H functionalizations catalyzed by either palladium or
o coppercatalysts,inwhichtheuseofmolecularoxygentoreactivatethecatalyst
d
he is highlighted.
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bli Finally,thelastchapterofthebook,Chapter12(Fairlamb),isdevotedtothe
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P synthesis of modified biomolecules by means of palladium-catalyzed cross-
coupling chemistry. Small nucleoside derivatization by C–X activation is
reported, as well as C-functionalization of larger biomolecules such as nucleic
acids, peptides and proteins. The use of biomolecules as substrates opens the
door to the synthesis of highly complex biomolecule targets.
Finally, I want to sincerely thank all the authors for their excellent
contributions,andforgivingmetheopportunitytotackleinthisbooksomeof
thehottesttopicsinmetal-catalyzedC–XandC–Hfunctionalizationstrategies,
whichinmyviewwillcompletelyalterthestrategiesinorganicsynthesisinthe
next years.
Xavi Ribas
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9/ Chapter 1 Cu-Catalyzed Ullmann-Type C–Heteroatom Bond
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10 Formation:TheKeyRoleofDinucleatingAncillaryLigands 1
10. YongwenJiang,LantingXu,ChenggangZhouandDaweiMa
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c. 1.2 C–N Bond Formation 5
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http://p 11..22..23 AArryyllaAtimonidaantidonVinylation of N-Heterocycles 1138
n 1.2.4 Cross-Coupling of Aryl Halides or Vinyl
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aded y 2013 1.2.5 CHraolisdse-CsowuitphlinHgyodfraAzirdyel HanadlidHeysdwraitzhinUereas, 23
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and Vinyl Halides 28
1.3.2 Cross-CouplingofArylHalideswithAliphatic
Alcohols 31
1.3.3 Direct Hydroxylation of Aryl Halides 32
1.4 C–S Bond Formation 32
1.4.1 The Formation of Thioethers 32
1.4.2 The Synthesis of Alkenylsulfides 34
1.4.3 Assembly of Aryl Sulfones 34
1.5 C–P Bond Formation 36
1.6 C–X Bond Formation 38
1.7 Conclusion 39
References 39
RSCCatalysisSeriesNo.11
C–HandC–XBondFunctionalization:TransitionMetalMediation
EditedbyXaviRibas
rTheRoyalSocietyofChemistry2013
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
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x Contents
Chapter 2 Mechanistic Understanding of Copper-Catalyzed
Aryl–HeteroatomBondFormation:DependenceonAncillary
Ligands 46
Alicia Casitas
09 2.1 Introduction 46
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49 2.4.1 Mechanism Involving s-Bond Metathesis 52
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81 2.4.2 Mechanism Involving p-Complexation 53
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9/9 2.4.3 One Electron Redox Processes via CuI/CuII:
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0. 2.4.4 Oxidative Addition/Reductive Elimination
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n htt Chapter 3 Fundamental Pd0/PdII Redox Steps in Cross-coupling
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aded y 2013 RHeeatecrtoiognesn:eHouosmtoogHeneetoeuros,geHnyeobruisdMHeocmhaongiesnteicouPsa–thways
nloMa for C–C Couplings 72
w4 Ian J. S. Fairlamb and Adam F. Lee
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Variants) 76
3.2.2 A Key Role for PdII Hydroxide Species in
Suzuki Cross-Coupling 78
3.2.3 Issues with the Purity of Pd Precatalysts 80
3.2.4 ‘Homeopathic Cross-couplings’ – An Unusual
Case? 82
3.3 Hybrid Homogeneous–Heterogeneous Catalytic
Cycles 84
3.3.1 Pd Leaching and Hybrid Behaviour 84
3.3.2 Trapping In Situ Generated Pd Nanoparticles 85
3.3.3 Encapsulated Pd Nanoparticles Possessing
Useful Catalytic Activity 87
3.3.4 Questions About the Active Catalyst Phase 89
3.4 Heterogeneous Cross-Coupling Reactions 91
3.4.1 Early Evidence for Heterogeneous Behaviour 91
3.4.2 Comparison of a Suzuki Cross-Coupling
Mediated by Pd(OAc) and (PVP)PdNPs 91
2