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Palladium‐Catalyzed Vinylation Of Organic Halides

R. F. Heck
Published 1982 · Chemistry

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The palladium-catalyzed vinylation of organic halides provides a very convenient method for forming carboncarbon bonds at unsubstituted vinylic positions. Generally the reaction does not require anhydrous or anaerobic conditions although it is advisable to limit access of oxygen when arylphosphines are used as a component of the catalyst. The transformation is valuable because it cannot be carried out in a single step by any other known method (except in certain Meerwein reactions). The organic halide employed is limited to aryl, heterocyclic, benzyl, or vinyl types, with bromides and iodides seen most often. Halides with an easily eliminated beta-hydrogen atom (i.e., alkyl derivatives) cannot be used since they form only olefins by elimination under the normal reaction conditions. The base needed may be a secondary or tertiary amine, sodium or potassium acetate, carbonate, or bicarbonate. When nucleophilic secondary amines are used as coreactants with most vinylic halides, a variation occurs that often produces tertiary allylic amines as major products. The catalyst is commonly palladium acetate, although palladium chloride or preformed triarylphosphine palladium complexes, as well as palladium on charcoal, have been used. A reactant, product, or solvent may serve as the ligand in reactions involving organic iodides, but generally a triarylphosphine or a secondary amine is required when organic bromides are used. The reaction, which occurs between ca. 50° and 160° proceeds homogeneously. Solvents such as acetonitrile, dimethylformamide, hexamethylphosphoramide, N-methylpyrrolidinone, and methanol have been used, but are often not necessary. The procedure is applicable to a very wide range of reactants and yields are generally good to excellent. Several variations of the reaction are known in which the organic halide is replaced by other reagents such as organometallics, diazonium salts, or aromatic hydrocarbons. These reactions are not discussed in detail, but are only briefly compared with the halide reaction. Other related reactions such as the palladium-catalyzed replacement of allylic substituents with carbanionic reagents, the palladium-promoted nucleophilic substitutions at olefinic carbons, and the numerous palladium-catalyzed coupling reactions of halides and organometallics are also beyond the scope of this review. The palladium-catalyzed vinylic substitution reaction has not yet received much attention from organic chemists, but its broad scope and simplicity demonstrate that it is a useful method for the synthesis of a variety of olefinic compounds. Keywords: palladium catalyst; vinylation; organic halides; scope; limitations; experimental procedures; vinylic substitution; ethylene; acrylic acid; butenol; methyl acrylate; styrene; pentadiene; acrolein dimethyl acetal; olefins
This paper references
10.1016/0040-4020(73)80045-6
Reaction of coordinated phosphines—II: Arylation of substituted olefins by palladium(II) acetate and triarylphosphine
T. Yamane (1973)
10.1016/0040-4020(79)80071-X
The palladium catalyzed thienylation of allylic alcohols with 2- and 3-bromothiophenes and their derivatives
Y. Tamaru (1979)
10.1246/BCSJ.50.1021
Palladium-catalyzed reaction of olefins and acetylenes with iodoferrocenes.
A. Kasahara (1977)
10.1246/BCSJ.44.581
Arylation of Olefin with Aryl Iodide Catalyzed by Palladium
T. Mizoroki (1971)
10.1016/S0022-328X(00)93747-1
Palladium-catalyzed phenylation of allylic 1-perfluoroalkyl alcohols
K. C. Werner (1977)
10.1002/CHIN.197947153
Enol thioethers in synthesis. Regiocontrolled arylation via organopalladium chemistry
B. Trost (1979)
10.1021/jo01320a005
Palladium-catalyzed vinylation of conjugated dienes
Babu A. Patel (1979)
10.1246/BCSJ.50.551
The Palladium-catalyzed Phenylation of Enol Esters with Iodobenzene
A. Kasahara (1977)
10.1002/CHIN.197848093
Palladium-catalyzed vinylic substitution reactions with heterocyclic bromides
W. Frank (1978)
10.1021/jo01337a012
Selective palladium-catalyzed vinylic substitutions with bromoiodo aromatics
J. E. Plevyak (1979)
10.1021/JO00979A024
Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides
R. Heck (1972)
10.1016/S0022-328X(00)96038-8
Alkylation of olefins with “alkylpalladium acetates” lacking β hydrogen substituents. Observation of an intramolecular shift of an acetatopalladium group in neophylpalladium acetate
R. Heck (1972)
10.1246/BCSJ.46.1505
Arylation of Olefin with Iodobenzene Catalyzed by Palladium
K. Mori (1973)
10.1021/JO00409A001
Palladium-catalyzed vinylic substitution with highly activated aryl halides
C. Ziegler (1978)
10.1021/JA00811A029
Organophosphinepalladium complexes as catalysts for vinylic hydrogen substitution reactions
H. A. Dieck (1974)
10.1021/JA00479A025
Allylic alkylation: nucleophilic attack on .pi.-allylpalladium complexes
B. Trost (1978)
10.1246/BCSJ.52.2609
Reaction of Diazonium Salts with Transition Metals. II. Palladiumcatalyzed Arylation of Ethylene with Arenediazonium Salts
K. Kikukawa (1979)
10.1021/JO00406A033
Palladium-catalyzed arylation of ethylene
J. E. Plevyak (1978)
10.1021/JA01300A088
The Reaction of Butylacetylene with Hydrogen Bromide1
C. A. Young (1936)
10.1021/JO00420A029
Palladium-catalyzed arylation of conjugated dienes
Babu A. Patel (1978)
10.1021/JO00864A017
Palladium-catalyzed arylation of allylic alcohols with aryl halides
J. B. Melpolder (1976)
10.1002/CHIN.197814185
Palladium-catalyzed vinylic substitution reactions with carboxylic acid derivatives
Babu A. Patel (1978)
10.1021/JO00319A005
Palladium-catalyzed synthesis of 2,4-dienoic acid derivatives from vinylic halides
J. Kim (1981)
10.1021/JA00469A031
Mercury in organic chemistry. 14. A convenient regiospecific synthesis of .pi.-allylpalladium compounds via vinylmercurials
R. Larock (1978)
10.1021/jo00411a032
Palladium-catalyzed reaction of 3-bromopyridine with allylic alcohols: a convenient synthesis of 3-alkylpyridines
Y. Tamaru (1978)
10.1002/CHIN.197619174
Palladium-catalyzed vinyl substitution reactions. I. New synthesis of 2- and 3-phenyl-substituted allylic alcohols, aldehydes, and ketones from allylic alcohols
A. Chalk (1976)
10.1246/BCSJ.48.1533
Intramolecular Oxypalladation. Cyclization Reaction of 2-Allylphenols with Palladium Salts
T. Hosokawa (1975)
10.1021/jo00444a024
Palladium-catalyzed arylation of unsaturated acetals and ketals
T. Zebovitz (1977)
10.1021/JO00872A002
Aromatic substitution of olefins. XXV. Reactivity of benzene, naphthalene, ferrocene, and furan toward styrene, and the substituent effect on the reaction of monosubstituted benzenes with styrene
Y. Fujiwara (1976)
10.1016/S0022-328X(00)91739-X
Arylation of the reformatsky reagent catalyzed by zerovalent complexes of palladium and nickel
J. Fauvarque (1977)
10.1021/JO00319A004
Palladium-catalyzed three carbon chain extension reactions with acrolein acetals. A convenient synthesis of conjugated dienals
Babu A. Patel (1981)
10.1021/AR50136A006
Palladium-catalyzed reactions of organic halides with olefins
R. Heck (1979)
10.1021/JA01022A036
Allylation of aromatic compounds with organopalladium salts
R. Heck (1968)
10.1016/S0022-328X(00)80437-4
Organo-iron and -cobalt phthalocyanines in alkylation and arylation of olefins
M. Vol’pin (1972)
10.1021/JA00511A032
Palladium-catalyzed coupling of tetraorganotin compounds with aryl and benzyl halides. Synthetic utility and mechanism
D. Milstein (1979)
10.1016/S0022-328X(00)82024-0
Palladium-promoted addition of amines to isolated double bonds
B. Akermark (1974)
10.1002/chin.197623330
SYNTHESIS OF C-5 SUBSTITUTED PYRIMIDINE NUCLEOSIDES VIA ORGANOPALLADIUM INTERMEDIATES
D. Bergstrom (1976)
10.1351/pac197850080691
New applications of palladium in organic syntheses
R. F. Heck (1978)
10.1021/jo01306a009
Reactions of .pi.-allylic palladium intermediates with amines
F. G. Stakem (1980)
10.1016/S0079-6468(08)70141-3
5 The Chemistry and Biochemistry of C-Nucleosides
G. Daves (1976)
10.1021/JA01022A034
Acylation, methylation, and carboxyalkylation of olefins by Group VIII metal derivatives
R. Heck (1968)
10.1021/JO00414A024
Palladium-catalyzed synthesis of allylic tertiary amines from vinylic bromides, olefins, and secondary amines
Babu A. Patel (1978)
10.1021/jo00409a003
Palladium-catalyzed vinylic substitution reactions of N-vinyl amides
C. Ziegler (1978)
10.1021/jo01315a005
Palladium-catalyzed phenylation of enol ethers and acetates
I. Arai (1979)
10.1246/BCSJ.46.2490
Palladium-Catalyzed Coupling Reaction of Aromatic Compounds
H. Yoshimoto (1973)
10.1016/S0022-328X(00)81489-8
The cleavage of SiC bonds by transition metal compounds. Methylation and phenylation of olefins by organosilicon compounds in the presence of palladium salts
I. S. Akhrem (1974)
10.1021/JO00896A020
Palladium-catalyzed conjugated diene synthesis from vinylic halides and olefinic compounds
H. A. Dieck (1975)



This paper is referenced by
10.1021/OL048140R
Three-component, stereoselective palladium-catalyzed synthesis of functionalized bicyclopentanoids.
Bernard Hulin (2004)
10.1002/ADSC.200600301
A Tandem, Nitroalkene Conjugate Addition/[3+2] Cycloaddition Approach to the Synthesis of the Pentacyclic Core of (±)‐Scandine
S. Denmark (2006)
10.1002/9780470048672.WECB651
Pharmaceutical Industry: Biocatalysts and Chemocatalysts
D. Ager (2008)
10.1016/J.JORGANCHEM.2008.06.020
Synthesis of 1,3-bis-(5-ferrocenylisoxazole-3-yl) benzene-derived palladium(II) acetate complex and its application in Mizoroki–Heck reaction in an aqueous solution
Yongjia Shang (2008)
10.1007/s00216-010-4555-1
The 2010 Chemistry Nobel Prize to R.F. Heck, E. Negishi, and A. Suzuki for palladium-catalyzed cross-coupling reactions
Didier Astruc (2011)
10.1002/CPLU.201100021
Palladium Nanoparticles Supported on Mixed-Linker Metal–Organic Frameworks as Highly Active Catalysts for Heck Reactions
Yuan-Biao Huang (2012)
10.1002/9781118498088.CH10
Synthesis of 3-Spiro-Substituted Nucleosides: Chemistry of TSAO Nucleoside Derivatives
María José Camarasa (2013)
10.1002/chem.201702354
A Highly Fluorinated Chiral Aldehyde for Enantioselective Fluorescent Recognition in a Biphasic System.
Chao Wang (2017)
10.1016/J.TET.2017.10.005
Regioselective monobromination of aromatics via a halogen bond acceptor-donor interaction of catalytic thioamide and N-bromosuccinimide
Pakorn Bovonsombat (2017)
10.1016/j.molstruc.2019.127448
Spectroscopic, structural, electronic and bioactive characteristics of 3,5-bis(2,5-dimethylphenyl)pyridine (1): An experimental and theoretical investigations
Muhammad Arslan Akram (2020)
10.1039/C8QO01388H
SO2F2 mediated dehydrative cross-coupling of alcohols with electron-deficient olefins in DMSO using a Pd-catalyst: one-pot transformation of alcohols into 1,3-dienes
Revathi Lekkala (2019)
10.1021/OL035184B
Homeopathic ligand-free palladium as a catalyst in the heck reaction. A comparison with a palladacycle.
A. D. de Vries (2003)
10.1016/J.TET.2005.03.008
Efficient and fast Heck vinylation of 2-bromo-6-methyl pyridines with methylacrylate. Application to the synthesis of 6-methyl cyclopenta[b]pyridinone
N. Robert (2005)
10.1016/J.TETLET.2007.02.078
Enantioselective synthesis of aminobenzazepinones
C. Prasad (2007)
10.1088/1674-0068/23/02/175-179
Ligand Size Effect on PdLn Oxidative Addition with Aryl Bromide: A DFT Study
Wenjing Sun (2010)
10.1002/ANGE.201100028
Zweihundert Jahre Iodforschung: ein interdisziplinärer Überblick über die derzeitige Forschung
Frithjof C. Küpper (2011)
10.1002/chem.201103171
Silanol as a removable directing group for the Pd(II)-catalyzed direct olefination of arenes.
Changchang Wang (2011)
10.1002/ANGE.201107017
Palladiumkatalysierte Kreuzkupplungen: eine historische Perspektive im Kontext der Nobel-Preise 2010
Carin C. C. Johansson Seechurn (2012)
10.1021/ic5014494
Practical synthesis of 1,12-difunctionalized o-carborane for the investigation of polar liquid crystals.
A. Jankowiak (2014)
10.1007/s11144-014-0735-x
Catalytic investigation of PdCl2(TDA)2 immobilized on hydrophobic graphite oxide in the hydrogenation of 1-pentyne and the Heck coupling reaction
Ágnes Mastalir (2014)
10.3762/bjoc.15.94
Heck- and Suzuki-coupling approaches to novel hydroquinone inhibitors of calcium ATPase
R. J. Kempton (2019)
10.1002/SLCT.201802282
SingaCycleTM‐A1‐Catalyzed Successive Suzuki‐Miyaura and Buchwald Couplings for the Synthesis of Various New Pyridine Analogues
Gokanapalli Anusha (2018)
10.1002/AIC.690490114
Reverse‐flow operation for application of imperfectly immobilized catalysts
Kim G. W. Hung (2003)
10.1016/S0022-328X(03)00668-5
Silica-supported bidentate arsine palladium(0) complex: a highly active and stereoselective catalyst for arylation of conjugated alkenes
Mingzhong Cai (2003)
10.1021/OL0483192
Oxygen-promoted palladium(II) catalysis: facile C(sp2)-C(sp2) bond formation via cross-coupling of alkenylboronic compounds and olefins.
C. H. Yoon (2004)
10.1002/ANGE.200462544
Kinetische Reaktionsfortschrittsanalyse: eine Methode zur mechanistischen Untersuchung komplexer katalytischer Reaktionen
D. G. Blackmond (2005)
10.1002/ANGE.19891010827
Selektive 1:3‐Kupplung von Norbornen und Iodbenzol; einfache Synthese Cycloaliphaten‐anellierter Benzo[e]pyrene
O. Reiser (2006)
10.1002/9783527619535.CH5
Cross‐Coupling of Organyl Halides with Alkenes – The Heck Reaction
S. Bräse (2008)
10.1002/chem.200901774
Regioselective arene functionalization: simple substitution of carboxylate by alkyl groups.
Tobias Krüger (2009)
10.1080/00268976.2010.486139
A theoretical investigation of the oxidation states of palladium complexes and their role in the carbonylation reaction
Andrea Bottoni (2010)
10.1021/ol300442w
Pd(II)-catalyzed dehydrogenative olefination of vinylic C-H bonds with allylic esters: general and selective access to linear 1,3-butadienes.
Yuexia Zhang (2012)
10.1002/anie.201510320
Synthesis of Nitrogen-Containing Rubicene and Tetrabenzopentacene Derivatives.
Y. Park (2016)
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