Arylation of Olefin with Aryl Iodide Catalyzed by Palladium
01 Feb 1971-Bulletin of the Chemical Society of Japan (The Chemical Society of Japan 公益社団法人 日本化学会)-Vol. 44, Iss: 2, pp 581-581
About: This article is published in Bulletin of the Chemical Society of Japan.The article was published on 1971-02-01 and is currently open access. It has received 1120 citations till now. The article focuses on the topics: Palladium & Aryl.
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TL;DR: s, or keywords if they used Heck-type chemistry in their syntheses, because it became one of basic tools of organic preparations, a natural way to make organic preparations.
Abstract: s, or keywords if they used Heck-type chemistry in their syntheses, because it became one of basic tools of organic preparations, a natural way to
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TL;DR: The Review presents the recent developments and the use of NP catalysis in organic synthesis, for example, in hydrogenation and C--C coupling reactions, and the heterogeneous oxidation of CO on gold NPs.
Abstract: Interest in catalysis by metal nanoparticles (NPs) is increasing dramatically, as reflected by the large number of publications in the last five years. This field, "semi-heterogeneous catalysis", is at the frontier between homogeneous and heterogeneous catalysis, and progress has been made in the efficiency and selectivity of reactions and recovery and recyclability of the catalytic materials. Usually NP catalysts are prepared from a metal salt, a reducing agent, and a stabilizer and are supported on an oxide, charcoal, or a zeolite. Besides the polymers and oxides that used to be employed as standard, innovative stabilizers, media, and supports have appeared, such as dendrimers, specific ligands, ionic liquids, surfactants, membranes, carbon nanotubes, and a variety of oxides. Ligand-free procedures have provided remarkable results with extremely low metal loading. The Review presents the recent developments and the use of NP catalysis in organic synthesis, for example, in hydrogenation and C--C coupling reactions, and the heterogeneous oxidation of CO on gold NPs.
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TL;DR: In this Review, highlights of a number of selected syntheses are discussed, demonstrating the enormous power of these processes in the art of total synthesis and underscore their future potential in chemical synthesis.
Abstract: In studying the evolution of organic chemistry and grasping its essence, one comes quickly to the conclusion that no other type of reaction plays as large a role in shaping this domain of science than carbon-carbon bond-forming reactions. The Grignard, Diels-Alder, and Wittig reactions are but three prominent examples of such processes, and are among those which have undeniably exercised decisive roles in the last century in the emergence of chemical synthesis as we know it today. In the last quarter of the 20th century, a new family of carbon-carbon bond-forming reactions based on transition-metal catalysts evolved as powerful tools in synthesis. Among them, the palladium-catalyzed cross-coupling reactions are the most prominent. In this Review, highlights of a number of selected syntheses are discussed. The examples chosen demonstrate the enormous power of these processes in the art of total synthesis and underscore their future potential in chemical synthesis.
2,268 citations
TL;DR: This Review attempts to trace the historical origin of these powerful reactions, and outline the developments from the seminal discoveries leading to their eminent position as appreciated and applied today.
Abstract: In 2010, Richard Heck, Ei-ichi Negishi, and Akira Suzuki joined the prestigious circle of Nobel Laureate chemists for their roles in discovering and developing highly practical methodologies for C-C bond construction. From their original contributions in the early 1970s the landscape of the strategies and methods of organic synthesis irreversibly changed for the modern chemist, both in academia and in industry. In this Review, we attempt to trace the historical origin of these powerful reactions, and outline the developments from the seminal discoveries leading to their eminent position as appreciated and applied today.
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TL;DR: This critical review covers the recent progresses on the regioselective dehydrogenative direct coupling reaction of heteroarenes, including arylation, olefination, alkynylation, and amination/amidation mainly utilizing transition metal catalysts.
Abstract: The direct functionalization of heterocyclic compounds has emerged as one of the most important topics in the field of metal-catalyzed C–H bond activation due to the fact that products are an important synthetic motif in organic synthesis, the pharmaceutical industry, and materials science. This critical review covers the recent progresses on the regioselective dehydrogenative direct coupling reaction of heteroarenes, including arylation, olefination, alkynylation, and amination/amidation mainly utilizing transition metal catalysts (113 references).
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References
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TL;DR: P palladium acetate was found to be the most effective for the direct arylation of olefins with aromatic compounds in the presence of acetic acid.
Abstract: Olefins react with benzene derivatives to produce aryl-substituted olefins uia direct substitution of the aromatic compound for hydrogen on the double bond of the olefin in the presence of palladium salts and reduced palladium metal. The reaction may be made catalytic with respect to the palladium salts by using cupric acetate or silver acetate, and air as reoxidants. The reaction provides an extremely convenient method for the synthesis of a wide variety of olefinic compounds. xtensive studies on reactions of olefins in the presE ence of transition metal compounds have been carried out. Much less is known about arylation of olefins with transition metal compounds. Most recently, Heck described interesting arylation reactions of olefins with arylating agents such as arylmercuric halides in the presence of group VI11 metal salts, and showed that palladium salts are the most generally useful, with rhodium and ruthenium salts next best. We have reported a novel method of synthesizing stilbene derivatives by substitution of aromatic compounds for hydrogen on the double bond of the styrenepalladium chloride ~ o m p l e x . ~ In the course of our work, palladium acetate was found to be the most effective for the direct arylation of olefins with aromatic compounds in the presence of acetic acid. The present paper reports a study of substitution reaction of olefins with benzene derivatives by means of palladium salts, especially palladium acetate. A preliminary communication of a portion of this work has been given.4 ( I ) On leave of absence from Ube Industries, Ltd., Ube, Japan. (2) (a) R. F. Heck, J . Amer. Chem. Soc., 90, 5518 (1968); (b) R .F. Heck, ibid., 90, 5526 (1968); (c) R. F. Heck, ibid., 90, 5531 (1968); (d) R. F. Heck, ibid., 90, 5535 (1968); (e) R. F. Heck, ibid., 90, 5542 (1968). (3) (a) I. Moritani and Y. Fujiwara, Tefrahedron L e f f . , 1119 (1967); (b) Y . Fujiwara, I. Moritani, and M. Matsuda, Tetrahedron, 24, 4819 (1968). (4) Y. Fujiwara, I. Moritani, M. Matsuda, and S . Teranishi, Tetrahedron Lett., 633 (1968). Results and Discussion In previous papers3 we described our initial work on the reactions of the styrene-palladium(I1) chloride complex with benzene derivatives to give stilbenes. It was noted that for this arylation on a P-carbon atom of styrene, the presence of a carboxylic acid such as acetic is essential because the reactants form a homogeneous solution and the reaction proceeds best in this solvent. Further, it was found that when sodium acetate was added, the yield was greatly increased. Palladium(I1) acetate has been found to be the most generally useful, with palladium(I1) chloride-sodium acetate next best for the direct arylation of olefins with benzene derivatives. The aromatic substitution of olefins takes place in homogeneous solutions of reactant olefin and palladium(I1) acetate (equal mole equivalents to olefin) in a solution of the aromatic compound (large excess) and acetic acid. The solution is stirred in the presence of air for a few minutes to several hours (8 hr usually), to give from 10% to ca. 90% yield of arylated products, with reduced metallic palladium and a very small amount of acetates. With unsymmetrical olefins, the aryl group generally adds predominantly to the less substituted carbon atom of the double bond because of steric hindrance of the substituents. This is consistent with that observed in the Heck arylation.2 Although cis and trans mixtures are formed, no mixtures resulting from arylation in both directions to unsymmetrical olefins have been found. Increasing substitution on the olefinic carbons decreases the reactivity of the olefin in the palladium acetate arylation reaction. For example, the reaction of triphenylethylene with benzene and a palladium acetate catalyst gave tetraphenylethylene in low yield (13 %),5 while styrene reacts with benzene to afford trans-stilbene in almost quantitative yield. Results are given in Table I. (5) Yields of arylation products given in this paper are based on the amount of palladium salt utilized. Journal of the American Chemical Soc ie t y J 91:25 December 3, 1969
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217 citations
TL;DR: In this paper, the effect of the salts of carboxylic acids and the course of the reaction are discussed. And the authors show that the rate of the carbonylation reaction of bromobenzene to form benzoic acid is proportional to bromo-benzene, nickel tetracarbonyl, and water and the reciprocal of the carbon monoxide pressure.
Abstract: In the reacion of aryl bromide with carbon monoxide in the presence of water and a catalytic amount of nickel carbonyl, it has been found that aromatic carboxylic acids (benzoic acid, polymethylbenzoic acid, α-naphthoic acid, etc.) are formed in very high yields when such salts of carboxylic acids as potassium acetate or sodium benzoate are added to the starting materials. The carbonylation reaction of aryl bromide is strongly inhibited by the hydrobromic acid formed, and the addition of the salt of carboxylic acid effectively decreases its concentration in the course of the reaction. When the amount of potassium acetate is larger than that of aryl bromide, the rate of the carbonylation reaction of bromobenzene to form benzoic acid is proportional to the amounts of bromo-benzene, nickel tetracarbonyl, and water and to the reciprocal of the carbon monoxide pressure. From these kinetic data, the effect of the salts of carboxylic acids and the course of the reaction are discussed.
9 citations