Online citations, reference lists, and bibliographies.

Mechanisms Of The Mizoroki–Heck Reaction

Anny Jutand
Published 2009 · Chemistry
Cite This
Download PDF
Analyze on Scholarcy
Share
The palladium-catalysed Mizoroki–Heck reaction is the most efficient route for the vinylation of aryl/vinyl halides or triflates. This reaction, in which a C C bond is formed, proceeds in the presence of a base (Scheme 1.1) [1, 2]. Nonconjugated alkenes are formed in reactions involving cyclic alkenes (Scheme 1.2) [1e, 2a,c,e,g] or in intramolecular reactions (Scheme 1.3) [2b,d–g] with creation of stereogenic centres. Asymmetric Mizoroki–Heck reactions may be performed in the presence of a chiral ligand [2]. The Mizoroki–Heck reaction has been intensively developed from a synthetic and mechanistic point of view, as expressed by the impressive number of reviews and book chapters [1, 2]. In the late 1960s, Heck reported that arylated alkenes were formed in the reaction of alkenes with a stoichiometric amount of [Ar–Pd Cl] or [Ar–Pd–OAc], generated in situ by reacting ArHgCl with PdCl2 or ArHgOAc with Pd(OAc)2 respectively [3]. A mechanism was proposed which involves a syn migratory insertion of the alkene into the Ar–Pd bond, followed by a syn β-hydride elimination of a hydridopalladium [HPdX] (X = Cl, OAc) (Scheme 1.4a). In the case of cyclic alkenes, in which no syn β-hydride is available, a syn β ′-hydride elimination occurs, leading to a nonconjugated alkene (Scheme 1.4b). Isomerization of the new C C bond may occur by a syn readdition of HPdX in the reverse direction, followed by a syn β ′′-hydride elimination (Scheme 1.4c) [3c].
This paper references
10.1016/0022-328X(83)89511-4
A highly efficient version of the palladium-catalysed arylation of alkenes with aryl bromides
Alwyn Spencer (1983)
10.1002/chin.199720062
Nickel‐ and Palladium‐Catalyzed Homocoupling of Aryl Triflates. Scope, Limitation, and Mechanistic Aspects.
Anny Jutand (2010)
10.1002/chem.200600153
Rate and mechanism of the reaction of alkenes with aryl palladium complexes ligated by a bidentate P,P ligand in Heck reactions.
Christian Amatore (2007)
10.1002/chem.19970030823
Palladacycles: Efficient New Catalysts for the Heck Vinylation of Aryl Halides†
Wolfgang Anton Herrmann (1997)
10.1002/chin.199011135
Catalytic Asymmetric C-C Bond Formation: Asymmetric Synthesis of cis-Decalin Derivatives by Palladium-Catalyzed Cyclization of Prochiral Alkenyl Iodides.
Yoshihiro Sato (1990)
10.1055/s-2006-951519
Reactivity of Pd(0)(NHC)2 (NHC: N-Heterocyclic Carbene) in Oxidative ­Addition with Aryl Halides in Heck Reactions
Sylvain Roland (2006)
The higher reactivity of alkenes with cationic trans-PhPdS(PMe3)2+ than with neutral
F. Kawataka (1995)
10.1016/S0040-4039(98)00398-0
The Heck olefination reaction; A DFT study of the elimination pathway
Robert J. Deeth (1998)
10.1002/anie.199424211
Palladacycles as Intermediates for Selective Dialkylation of Arenes and Subsequent Fragmentation
Marta Catellani (1995)
10.3891/acta.chem.scand.52-0100
Evidence for an Equilibrium between Neutral and Cationic Arylpalladium(II) Complexes in DMF. Mechanism of the Reduction of Cationic Arylpalladium(II) Complexes.
Christian Amatore (1998)
10.1021/ja00124a026
Oxidative Addition of Aryl Bromide after Dissociation of Phosphine from a Two-Coordinate Palladium(0) Complex, Bis(tri-o-tolylphosphine)Palladium(0)
John F. Hartwig (1995)
10.1002/anie.199623591
A Route to Pdo from PdII Metallacycles in Animation and Cross‐Coupling Chemistry
Janis Louie (1996)
10.1002/anie.199518441
Palladacycles as Structurally Defined Catalysts for the Heck Olefination of Chloro‐ and Bromoarenes
Wolfgang Anton Herrmann (1995)
10.1002/chem.19960020708
N‐Heterocyclic Carbenes: Generation under Mild Conditions and Formation of Group 8–10 Transition Metal Complexes Relevant to Catalysis
Wolfgang Anton Herrmann (1996)
For DFT calculations on a related anionic
L. J. Goossen (2004)
10.1002/adsc.200404218
A Novel Water-Soluble m-TPPTC Ligand: Steric and Electronic Features –Recent Developments in Pd- and Rh-Catalyzed CC Bond Formations
Emilie Génin (2004)
10.1002/anie.199709841
Intermediates in the Intermolecular, Asymmetric Heck Arylation of Dihydrofurans
King Kuok Mimi Hii (1997)
10.1246/bcsj.44.581
Arylation of Olefin with Aryl Iodide Catalyzed by Palladium
Tsutomu Mizoroki (1971)
Arylation, methylation, and carboxyalkylation of olefins by Group VIII metal derivatives
R. F. Heck (1968)
10.1016/s0022-328x(99)00590-2
N-Heterocyclic carbenes
Volker P. W. Boehm (2000)
10.1002/ejic.200300069
The Use of Conductivity Measurements for the Characterization of Cationic Palladium(II) Complexes and for the Determination of Kinetic and Thermodynamic Data in Palladium-Catalyzed Reactions
Anny Jutand (2003)
10.1016/S0022-328X(03)00476-5
Chiral diaminocarbene palladium(II) complexes: synthesis, reduction to Pd(0) and activity in the Mizoroki–Heck reaction as recyclable catalysts
Julien Pytkowicz (2003)
10.1016/j.jorganchem.2005.07.117
Oxidative addition of aryl chlorides to palladium N-heterocyclic carbene complexes and their role in catalytic arylamination
Jennifer C. Green (2005)
10.1039/A709028E
Speculations on new mechanisms for Heck reactions
Bernard L. Shaw (1998)
10.1055/s-2000-7919
A New Efficient Palladium Catalyst for Heck Reactions of Deactivated Aryl Chlorides
Andreas Ehrentraut (2000)
For the formation of major Pd(dba)L2 complexes when L is not a bulky phosphine, see: Amatore, C. and Jutand, A
J. Yin (1998)
10.1002/anie.199523711
Metal Complexes of N‐Heterocyclic Carbenes—A New Structural Principle for Catalysts in Homogeneous Catalysis
Wolfgang Anton Herrmann (1995)
10.1002/chin.199925062
Heck Reactions in the Presence of P(t-Bu)3: Expanded Scope and Milder Reaction Conditions for the Coupling of Aryl Chlorides.
Adam F. Littke (1999)
10.1021/om9809771
Zerovalent palladium and nickel complexes of heterocyclic carbenes: Oxidative addition of organic halides, carbon-carbon coupling processes, and the Heck reaction
David S. McGuinness (1999)
10.1002/adsc.200404072
Conformationally Restricted Arene Intermediates in the Intermolecular Heck Arylation of Vinylarenes
King Kuok Mimi Hii (2004)
10.1021/om020439v
Decelerating Effect of Alkenes in the Oxidative Addition of Phenyl Iodide to Palladium(0) Complexes in Heck Reactions
Christian Amatore (2002)
10.1021/om9803265
An Exploratory Study of Regiocontrol in the Heck Type Reaction. Influence of Solvent Polarity and Bisphosphine Ligands
Maik Ludwig (1999)
The beneficial role of dba in the formation of the Pd(0) complex is not quite clear, but alkenes are known to favour reductive elimination
R. Giovannini (1998)
10.1002/1521-3773(20020517)41:10<1760::AID-ANIE1760>3.0.CO;2-3
Profound steric control of reactivity in aryl halide addition to bisphosphane palladium(0) complexes.
Erwan Galardon (2002)
10.1021/om00004a039
Rates and Mechanism of the Formation of Zerovalent Palladium Complexes from Mixtures of Pd(OAc)2 and Tertiary Phosphines and Their Reactivity in Oxidative Additions
Christian Amatore (1995)
10.1021/om00012a029
EVIDENCE FOR THE LIGATION OF PALLADIUM(0) COMPLEXES BY ACETATE IONS : CONSEQUENCES ON THE MECHANISM OF THEIR OXIDATIVE ADDITION WITH PHENYL IODIDE AND PHPD(OAC)(PPH3)2 AS INTERMEDIATE IN THE HECK REACTION
Christian Amatore (1995)
10.1016/S0022-328X(00)00722-1
Synthesis, structure and catalytic application of palladium(II) complexes bearing N-heterocyclic carbenes and phosphines ☆
Wolfgang Anton Herrmann (2001)
Principles and Applications of Organotransition Metal Chemistry, University Science Books
J. P. Collman (1987)
10.1002/anie.199606571
Characterization of Reactive Intermediates in Palladium‐Catalyzed Arylation of Methyl Acrylate (Heck Reaction)
John Mason Brown (1996)
10.1021/om9906417
Factors Affecting the Oxidative Addition of Aryl Electrophiles to 1,1‘-Bis(diphenylphosphino)ferrocenepalladium(η2-methyl acrylate), an Isolable Pd[0] Alkene Complex
Anny Jutand (1999)
Evidence of the formation of zerovalent palladium from Pd(OAc)2 and triphenylphosphine
C. Amatore (1992)
For the synthesis of Pd(carbene)2 with C C unsaturated carbenes
P. L. Arnold (1999)
10.1021/ja035565k
Synthetic, structural, and mechanistic studies on the oxidative addition of aromatic chlorides to a palladium (N-heterocyclic carbene) complex: relevance to catalytic amination.
Alexandra K. de K. Lewis (2003)
10.1021/ja983419m
A Fluorescence-Based Assay for High-Throughput Screening of Coupling Reactions. Application to Heck Chemistry
Kevin H Shaughnessy (1999)
10.1021/jo00220a042
The effect of added silver nitrate on the palladium-catalyzed arylation of allyltrimethylsilanes
Kostas Karabelas (1985)
10.1007/978-3-642-67475-4
Organic synthesis with palladium compounds
Jiro Tsuji (1975)
10.1002/chin.197848092
PALLADIUM‐CATALYZED VINYLIC SUBSTITUTION WITH HIGHLY ACTIVATED ARYL HALIDES
G. B. Jun. Ziegler (1978)
10.1021/om9709190
On C−C Coupling by Carbene-Stabilized Palladium Catalysts: A Density Functional Study of the Heck Reaction
Katrin Albert (1998)
10.1021/ja00961a043
Allylic Oxidation of Olefins by Palladium Acetate1
William Kitching (1966)
10.1002/1521-3765(20011001)7:19<4191::AID-CHEM4191>3.0.CO;2-1
Mechanism of the Heck reaction using a phosphapalladacycle as the catalyst: classical versus palladium(IV) intermediates.
Volker P. W. Boehm (2001)
10.1021/om0101137
Formation of Palladium(0) Complexes from Pd(OAc)2 and a Bidentate Phosphine Ligand (dppp) and Their Reactivity in Oxidative Addition
Christian Amatore (2001)
10.1002/1099-0682(200008)2000:8<1855::AID-EJIC1855>3.0.CO;2-#
Reversible Formation of a Cationic Palladium(II) Hydride [HPd(PPh3)2]+ in the Oxidative Addition of Acetic or Formic Acid to Palladium(0) in DMF
Christian Amatore (2000)
10.1021/om020552l
The first example of simple oxidative addition of an aryl chloride to a discrete palladium N-heterocyclic carbene amination precatalyst
Stephen Caddick (2002)
10.1246/bcsj.46.1505
Arylation of Olefin with Iodobenzene Catalyzed by Palladium
Kunio Mori (1973)
10.1021/om00021a021
Reactions of Electron-Rich Arylpalladium Complexes with Olefins. Origin of the Chelate Effect in Vinylation Catalysis
Moshe Portnoy (1994)
10.1246/cl.1992.2177
Generation of Tertiary Phosphine-Coordinated Pd(0) Species from Pd(OAc)2 in the Catalytic Heck Reaction
Fumiyuki Ozawa (1992)
10.1351/pac199264030421
Catalytic asymmetric arylation of olefins
Tamio Hayashi (1992)
10.1002/1521-3765(20010417)7:8<1703::AID-CHEM17030>3.0.CO;2-K
Computational study of a new heck reaction mechanism catalyzed by palladium(II/IV) species.
Andreas Sundermann (2001)
10.1021/ol035184b
Homeopathic ligand-free palladium as a catalyst in the heck reaction. A comparison with a palladacycle.
André H M de Vries (2003)
Electronic control in the regiochemistry in the Heck reaction
H. Von Schenck (2003)
10.1021/ja0471424
Elucidating reactivity differences in palladium-catalyzed coupling processes: the chemistry of palladium hydrides.
Ivory D. Hills (2004)
10.1002/chin.197417128
ORGANOPHOSPHINEPALLADIUM COMPLEXES AS CATALYSTS FOR VINYLIC HYDROGEN SUBSTITUTION REACTIONS
Harold A. Dieck (1974)
10.1021/ja042959i
Distinct mechanisms for the oxidative addition of chloro-, bromo-, and iodoarenes to a bisphosphine palladium(0) complex with hindered ligands.
Fabiola Barrios-Landeros (2005)
10.1055/s-2006-951527
Interplays between Reactions within and without the Catalytic Cycle of the Heck Reaction as a Clue to the Optimization of the Synthetic Protocol
Alexander Schmidt (2006)
10.1021/jo00979a024
Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides
Richard F. Heck (1972)
10.1021/om00004a038
Rate and Mechanism of Oxidative Addition of Aryl Triflates to Zerovalent Palladium Complexes. Evidence for the Formation of Cationic (.sigma.-Aryl)palladium Complexes
Anny Jutand (1995)
10.1002/(SICI)1521-3773(20000103)39:1<165::AID-ANIE165>3.0.CO;2-B
Phosphane-Free Palladium-Catalyzed Coupling Reactions: The Decisive Role of Pd Nanoparticles.
Reetz (2000)
10.1021/om00029a052
Alkali-induced disproportionation of palladium(II) tertiary phosphine complexes, [L2PdCl2], to LO and palladium(O). Key intermediates in the biphasic carbonylation of ArX catalyzed by [L2PdCl2]
Vladimir V. Grushin (1993)
10.1039/C19680000006
Oxidative additions to palladium(0)
Peter Fitton (1968)
10.1016/S0022-328X(00)86726-1
Kinetics of oxidative addition of zerovalent palladium to aromatic iodides
Jean-François Fauvarque (1981)
10.1002/chem.200306056
Active anionic zero-valent palladium catalysts: characterization by density functional calculations.
Sebastian Kozuch (2004)
10.1021/jo00126a037
NEW SYNTHETIC APPLICATIONS OF WATER-SOLUBLE ACETATE PD/TPPTS CATALYST GENERATED IN SITU. EVIDENCE FOR A TRUE PD(0) SPECIES INTERMEDIATE
Christian Amatore (1995)
FORMATION OF ZEROVALENT PALLADIUM FROM THE CATIONIC COMPLEX PD(PPH3)2(BF4)2 IN THE PRESENCE OF PPH3 AND WATER IN DMF
Christian Amatore (1996)
10.1016/j.tet.2005.07.098
In situ formation of palladium(0) from a P,C-palladacycle
Fanny d’Orlyé (2005)
10.1021/om0610849
Rate and Mechanism of the Heck Reactions of Arylpalladium Complexes Ligated by a Bidentate P,P Ligand with an Electron-Rich Alkene (Isobutyl Vinyl Ether)
Christian Amatore (2007)
10.1021/ol015827s
Highly efficient Heck reactions of aryl bromides with n-butyl acrylate mediated by a palladium/phosphine-imidazolium salt system.
Chuluo Yang (2001)
10.1016/j.jorganchem.2004.05.012
Formation of anionic palladium(0) complexes ligated by the trifluoroacetate ion and their reactivity in oxidative addition
Christian Amatore (2004)



This paper is referenced by
10.1016/J.MOLLIQ.2017.02.053
Insight into acidity driven third phase formation of TBP in organic solutions by MD simulation
Meena B. Singh (2017)
10.1002/9783527819201.ch4
Development of a Nickel‐Catalyzed Enantioselective Mizoroki–Heck Coupling
Jean-Nicolas Desrosiers (2020)
10.1021/acs.joc.5b00386
Palladium-meta-terarylphosphine catalyst for the Mizoroki-Heck reaction of (hetero)aryl bromides and functional olefins.
Daniel Weiliang Tay (2015)
10.1002/ADSC.201900572
Visible Light‐Induced Regioselective Decarboxylative Alkylation of the C(sp2)−H Bonds of Non‐Aromatic Heterocycles
Lixin Liu (2019)
10.1007/s11172-019-2490-7
The role of phosphine ligands in the catalytic systems of the Heck reaction with aromatic carboxylic anhydrides
N. A. Lagoda (2019)
10.1002/jssc.201800342
Quantification of eight active ingredients in crude and processed radix polygoni multiflori applying miniaturized matrix solid-phase dispersion microextraction followed by UHPLC.
Kun-Ze Du (2018)
10.3762/bjoc.10.249
Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions
Matthieu Jouffroy (2014)
Utilisation d'alcènes fluorés pour la synthèse et la fonctionnalisation de dérivés (hétéro)aromatiques et de composés phosphorés
Kevin Rousée (2017)
Detailed Study of the Mechanism of Heck Reaction Pre-activation of Palladium Catalyst
()
10.1007/s10973-019-08881-7
Thermal analysis of halogenated rubber cured with a new cross-linking system
Anna Dziemidkiewicz (2019)
Design and Synthesis of potent benzimidazolone HIV Non-nucleoside reverse transcriptase inhibitors
Nicole Pribut (2018)
10.1002/QUA.25912
Mechanistic study on iron(II)‐mediated direct arylation of benzene with chlorobenzene
Xiaoli Sun (2019)
10.1016/j.polymertesting.2020.106354
Reaction mechanism of halogenated rubber crosslinking using a novel environmentally friendly curing system
Anna Dziemidkiewicz (2020)
Olefin Addition to the Palladium Complex
()
10.1515/pac-2018-1225
Heterogeneous palladium SALOPHEN onto porous polymeric microspheres as catalysts for heck reaction
Claudio Mella (2019)
Continuous-flow synthesis of CF3-vinylic compounds via Heck-type coupling
Léon J.A. Spijkers (2014)
10.1021/la402480f
Palladium-catalyzed coupling reactions for the functionalization of Si surfaces: superior stability of alkenyl monolayers.
Gillian Collins (2013)
10.1002/anie.201710241
A Nickel-Catalyzed Carbonyl-Heck Reaction.
Jaya Kishore Vandavasi (2017)
Semantic Scholar Logo Some data provided by SemanticScholar