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Special Issue "Heck Coupling"

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Synthesis".

Deadline for manuscript submissions: closed (31 January 2010)

Special Issue Editor

Guest Editor
Prof. Dr. Cinzia Chiappe

Dipartimento di Chimica e Chimica Industriale, University of Pisa, c/o via Bonanno 33, 56126 Pisa, Italy
E-Mail
Fax: +39 050 2219660
Interests: Pd promoted cross couplings, regioselectivity of inter- and intramolecular reactions, catalyst developments, neoteric solvents, Heck reactions in solid phases, continuous processes, waste-minimized processes

Keywords

  • Pd promoted cross couplings
  • Regioselectivity of inter- and intramolecular reactions
  • Catalyst developments
  • Neoteric solvents
  • Heck reactions in solid phases
  • Continuous processes
  • Waste-minimized processes

Published Papers (9 papers)

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Research

Jump to: Review

Open AccessArticle Selective Heck Arylation of Cyclohexene with Homogeneous and Heterogeneous Palladium Catalysts
Molecules 2010, 15(4), 2166-2177; doi:10.3390/molecules15042166
Received: 27 January 2010 / Revised: 10 March 2010 / Accepted: 23 March 2010 / Published: 25 March 2010
Cited by 13 | PDF Full-text (415 KB)
Abstract
Palladium catalysts containing Pd(II) supported on Al2O3 and alumina-based mixed oxides, Al2O3-ZrO2, Al2O3-CeO2, and Al2O3-Fe2O3, are very effective in the
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Palladium catalysts containing Pd(II) supported on Al2O3 and alumina-based mixed oxides, Al2O3-ZrO2, Al2O3-CeO2, and Al2O3-Fe2O3, are very effective in the Heck coupling of iodobenzene with cyclohexene in DMF solution. The best results, up to 81% of monoarylated products with a selectivity to 4-phenylcyclohexene (3) close to 90% were obtained with KOH as a base. The catalytic activity of palladium supported on alumina-based oxides was compared with that of homogeneous precursors, such as Pd(OAc)2 and PdCl2(PhCN)2, used in [Bu4N]Br as the reaction medium. Under such conditions homogeneous systems were more selective and produced up to 60% of monoarylated products with a selectivity to 3 close to 60%. Full article
(This article belongs to the Special Issue Heck Coupling)
Figures

Open AccessArticle Reductive Heck Reactions of N-Methyl-substituted Tricyclic Imides
Molecules 2010, 15(3), 1302-1308; doi:10.3390/molecules15031303
Received: 30 January 2010 / Revised: 10 February 2010 / Accepted: 2 March 2010 / Published: 4 March 2010
Cited by 19 | PDF Full-text (259 KB)
Abstract The palladium-catalyzed hydroarylation of N-methyl-substituted tricyclic imides was studied in order to find a new stereoselective access to a series of new exo-aryl(hetaryl)-substituted tricyclic N-methylimides. Full article
(This article belongs to the Special Issue Heck Coupling)
Open AccessArticle Palladium-Catalyzed Heck Coupling Reaction of Aryl Bromides in Aqueous Media Using Tetrahydropyrimidinium Salts as Carbene Ligands
Molecules 2010, 15(2), 649-659; doi:10.3390/molecules15020649
Received: 16 December 2009 / Revised: 1 January 2010 / Accepted: 12 January 2010 / Published: 28 January 2010
Cited by 12 | PDF Full-text (214 KB)
Abstract
An efficient and stereoselective catalytic system for the Heck cross coupling reaction using novel 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts (1, LHX) and Pd(OAc)2 loading has been reported. The palladium complexes derived from the salts 1a-f prepared in situ exhibit good catalytic activity
[...] Read more.
An efficient and stereoselective catalytic system for the Heck cross coupling reaction using novel 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts (1, LHX) and Pd(OAc)2 loading has been reported. The palladium complexes derived from the salts 1a-f prepared in situ exhibit good catalytic activity in the Heck coupling reaction of aryl bromides under mild conditions. Full article
(This article belongs to the Special Issue Heck Coupling)
Open AccessArticle Palladium(II)/Cationic 2,2’-Bipyridyl System as a Highly Efficient and Reusable Catalyst for the Mizoroki-Heck Reaction in Water
Molecules 2010, 15(1), 315-330; doi:10.3390/molecules15010315
Received: 18 December 2009 / Revised: 8 January 2009 / Accepted: 12 January 2010 / Published: 12 January 2010
Cited by 33 | PDF Full-text (178 KB)
Abstract
A water-soluble and air-stable Pd(NH3)2Cl2/cationic 2,2’-bipyridyl system was found to be a highly-efficient and reusable catalyst for the coupling of aryl iodides and alkenes in neat water using Bu3N as a base. The reaction was
[...] Read more.
A water-soluble and air-stable Pd(NH3)2Cl2/cationic 2,2’-bipyridyl system was found to be a highly-efficient and reusable catalyst for the coupling of aryl iodides and alkenes in neat water using Bu3N as a base. The reaction was conducted at 140 °C in a sealed tube in air with a catalyst loading as low as 0.0001 mol % for the coupling of activated aryl iodides with butyl and ethyl acrylates, providing the corresponding products in good to excellent yields with very high turnover numbers. In the case of styrene, Mizoroki-Heck coupling products were obtained in good to high yields by using a greater catalyst loading (1 mol %) and TBAB as a phase-transfer agent. After extraction, the residual aqueous solution could be reused several times with only a slight decrease in its activity, making the Mizoroki-Heck reaction “greener”. Full article
(This article belongs to the Special Issue Heck Coupling)
Open AccessArticle Coupling Reactions of α-Bromocarboxylate with Non-Aromatic N-Heterocycles
Molecules 2009, 14(8), 3019-3029; doi:10.3390/molecules14083019
Received: 20 July 2009 / Revised: 30 July 2009 / Accepted: 12 August 2009 / Published: 13 August 2009
Cited by 3 | PDF Full-text (293 KB) | HTML Full-text | XML Full-text
Abstract
The conditions for the C-N bond forming reaction (C-N coupling reaction) between α-bromocarboxylate and nitrogen-containing non-aromatic heterocyclic rings under heterogeneous copper(I) oxide catalysis are investigated in this paper. All the generated compounds were fully characterized by IR, NMR and MS spectroscopy. Ab initio
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The conditions for the C-N bond forming reaction (C-N coupling reaction) between α-bromocarboxylate and nitrogen-containing non-aromatic heterocyclic rings under heterogeneous copper(I) oxide catalysis are investigated in this paper. All the generated compounds were fully characterized by IR, NMR and MS spectroscopy. Ab initio/DFT calculations of partial charges on nitrogen atoms in all the discussed heterocycles and on C(2) of carboxylate under applied conditions were predicted. These in silico results correlate relatively with the experimental observations. Full article
(This article belongs to the Special Issue Heck Coupling)

Review

Jump to: Research

Open AccessReview The Hydroarylation Reaction—Scope and Limitations
Molecules 2010, 15(5), 3402-3410; doi:10.3390/molecules15053402
Received: 25 February 2010 / Revised: 30 April 2010 / Accepted: 6 May 2010 / Published: 10 May 2010
Cited by 16 | PDF Full-text (227 KB)
Abstract
The synthetic potential of stereoselective, palladium-catalyzed hydro(het)arylation reactions of bi-, tri- and tetracyclic (hetero)alkenes in the presence of phospines and arsines as highly efficient ligands was studied. The mechanism of this reductive Heck reaction becomes more complex in the case of benzonorbornenes. Hydroarylation
[...] Read more.
The synthetic potential of stereoselective, palladium-catalyzed hydro(het)arylation reactions of bi-, tri- and tetracyclic (hetero)alkenes in the presence of phospines and arsines as highly efficient ligands was studied. The mechanism of this reductive Heck reaction becomes more complex in the case of benzonorbornenes. Hydroarylation of diazabicyclo-[2.2.1]heptenes provides a stereoselective access to aryldiaminocyclopentanes. Electron-deficient arylpalladium complexes shift the reaction towards the product of a formal 1,2-hydrazidoarylation reaction of 1,3-cyclopentadiene by a stereoselective C-N cleavage. Due to steric reasons, rigid bicyclo[2.2.2]octenes react slower in hydroarylation reactions than the corresponding bicyclo[2.2.1]heptenes. The more flexible bicyclo[4.2.2]decene system already tends to undergo domino-Heck reactions, even under reductive conditions. When a tetracyclic cis-allylcyclopropane is carbopalladated in the presence of formates, the neighboring cyclopropane ring is attacked in the first reported example of a π,σ domino-Heck reaction. Full article
(This article belongs to the Special Issue Heck Coupling)
Open AccessReview The Heck Reaction Applied to 1,3- and 1,2-Unsaturated Derivatives, a Way towards Molecular Complexity
Molecules 2010, 15(4), 2667-2685; doi:10.3390/molecules15042667
Received: 1 February 2010 / Revised: 26 March 2010 / Accepted: 1 April 2010 / Published: 13 April 2010
Cited by 38 | PDF Full-text (378 KB)
Abstract
This review is an overview of the last ten years’ use of the Mizoroki–Heck coupling applied to 1,2- and 1,3-dienes. Since both these systems form π-allyl palladium intermediates in Pd(0) coupling, they show particular chemical behavior. Many examples of 1,2-dienes Heck reactions are
[...] Read more.
This review is an overview of the last ten years’ use of the Mizoroki–Heck coupling applied to 1,2- and 1,3-dienes. Since both these systems form π-allyl palladium intermediates in Pd(0) coupling, they show particular chemical behavior. Many examples of 1,2-dienes Heck reactions are presented. 1,2-Dienes are important substrates because of their high reactivity that makes them useful building blocks for the synthesis of biologically relevant structures. Full article
(This article belongs to the Special Issue Heck Coupling)
Open AccessReview The Heck Reaction in Ionic Liquids: Progress and Challenges
Molecules 2010, 15(4), 2211-2245; doi:10.3390/molecules15042211
Received: 3 March 2010 / Revised: 22 March 2010 / Accepted: 26 March 2010 / Published: 30 March 2010
Cited by 60 | PDF Full-text (1077 KB)
Abstract
As the interest for environmental increases and environmental laws become more stringent, the need to replace existing processes with new more sustainable technologies becomes a primary objective. The use of ionic liquids to replace organic solvents in metal catalyzed reactions has recently gained
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As the interest for environmental increases and environmental laws become more stringent, the need to replace existing processes with new more sustainable technologies becomes a primary objective. The use of ionic liquids to replace organic solvents in metal catalyzed reactions has recently gained much attention and great progress has been accomplished in this area in the last years. This paper reviews the recent developments in the application of ionic liquids and related systems (supported ionic liquids, ionic polymers, and so on) in the Heck reaction. Merits and achievements of ionic liquids were analyzed and discussed considering the possibility of increasing the effectiveness of industrial processes. Full article
(This article belongs to the Special Issue Heck Coupling)
Open AccessReview Pd(II)/HPMoV-Catalyzed Direct Oxidative Coupling Reaction of Benzenes with Olefins
Molecules 2010, 15(3), 1487-1500; doi:10.3390/molecules15031487
Received: 15 January 2010 / Revised: 2 February 2010 / Accepted: 8 March 2010 / Published: 9 March 2010
Cited by 17 | PDF Full-text (255 KB)
Abstract
The direct aerobic coupling reaction of arenes with olefins was successfully achieved by the use of Pd(OAc)2/molybdovanadophosphoric acid (HPMoV) as a key catalyst under 1 atm of dioxygen. This catalytic system could be extended to the coupling reaction of various substituted
[...] Read more.
The direct aerobic coupling reaction of arenes with olefins was successfully achieved by the use of Pd(OAc)2/molybdovanadophosphoric acid (HPMoV) as a key catalyst under 1 atm of dioxygen. This catalytic system could be extended to the coupling reaction of various substituted benzenes with olefins such as acrylates, aclrolein, and ethylene through the direct aromatic C-H bond activation. Full article
(This article belongs to the Special Issue Heck Coupling)

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