A New Efficient Synthesis of the Stilbenoid Laser Dyes BPS and Stilbene I by Palladium‐Catalyzed Coupling of Ethene with Bromoarenes

Rümper, Jörg; Соколов, В. В.; Rauch, Karsten; Meijere, Armin de

doi:10.1002/cber.19971300905

Cited by 12 publications

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“…The spectroscopic data are in agreement with the reported values. [35] 4-Propenyl biphenyl (63):According to Procedure L, the polymer-bound biphenylaldehyde (39, …”

mentioning

confidence: 99%

Development of the Traceless Phenylhydrazide Linker for Solid‐Phase Synthesis

Stieber¹,

Grether²,

Waldmann³

2003

Chemistry A European J

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The hydrazide group is a new oxidatively cleavable traceless linker for solid-phase chemistry. It can be readily introduced by hydrazide formation between a carboxy-functionalized resin and different substituted hydrazines. In order to achieve high yields in this step, new carboxylic acid resins were developed that are not prone to undesired imide formation upon activation of the carboxylic acid. The polymer-bound acyl hydrazides were successfully employed in various transformations, namely Heck, Suzuki, Sonogashira, and Stille couplings, as well as Wittig and Grignard reactions. Traceless release of the coupling products from the solid support is achieved selectively under mild conditions and in high purity by oxidation of the aryl hydrazides to acyl diazenes with Cu(II) salts or N-bromosuccinimide (NBS) and subsequent nucleophilic attack of the acyl diazene intermediates. Traceless cleavage by oxidation with NBS can be carried out as a two-step process in which stable acyl diazenes are first generated by treatment with NBS in the absence of a nucleophile. After removal of the reagents by simple resin washing, the traceless release is effected by the addition of methanol, which leads to products of high purity without any additional separation steps.

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“…The spectroscopic data are in agreement with the reported values. [35] 4-Propenyl biphenyl (63):According to Procedure L, the polymer-bound biphenylaldehyde (39, …”

mentioning

confidence: 99%

Development of the Traceless Phenylhydrazide Linker for Solid‐Phase Synthesis

Stieber¹,

Grether²,

Waldmann³

2003

Chemistry A European J

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“…The coupling of ethylene to a variety of bromoarenes is an elegant approach to substituted styrenes, and the twofold coupling of ethene can even give stilbenes such as 12-SO 3 H, which was commonly used as a laser dye, in good yields. The ratio between formed styrene and stilbene depends on the ethylene excess, which can be controlled by the applied pressure (Scheme 8.3) [111]. Oligovinylarenes can be prepared from 1,2-(cf.…”

Section: The Alkenesmentioning

confidence: 99%

“…Dipotassium (E)-4,4 -Diphenylstilbene-4 ,4 -disulfonate (Stilbene I) (12-SO 3 K)Typical procedure for the Heck reaction of aryl bromides with ethene[111]: A 1 l glass autoclave was charged with a magnetic stirring bar as well as a mixture of 4 -bromobiphenyl-4-sulfonic acid (11-SO 3 H) (172 g, 0.55 mol), sodium 3-(diphenylphosphinyl)benzenesulfonate (3.78 g, 10.4 mmol), and demineralized water (174 ml). The autoclave was cooled with ice water, while triethylamine (189 ml, 1.36 mol) was added slowly with manual stirring until the solids had dissolved.…”

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confidence: 99%

Cross‐Coupling of Organyl Halides with Alkenes – The Heck Reaction

Bräse¹,

Meijere²

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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The carbopalladation of an alkene by an organylpalladium halide is the essential step in one of the major contemporary metal-catalyzed C-C coupling reactions. About 45 years ago, a Japanese and an American group almost simultaneously designed and executed palladium-mediated coupling reactions of aryl and alkenyl halides with alkenes [1]. In subsequent investigations, Richard Heck and his group developed this reaction into a catalytic transformation and started to demonstrate its usefulness as well as its rather broad scope. The real push to utilize this powerful C-C-bondforming process, however, started only around the mid-1980s, and by now, an impressive number of publications have established the meanwhile so-called Heck reaction [2] 1) as an indispensable method in Organic Synthesis [3][4][5][6][7]. The universal recognition of the importance of the Heck reaction and the Negishi as well as the Suzuki coupling eventually won the Nobel Prize for Richard Heck along with Ei-ichi Negishi and Akira Suzuki in 2010. The applications of the Heck reaction range from the preparation of -functionalized and unfunctionalized -hydrocarbons, novel polymers, and dyes to new advanced enantioselective syntheses of natural products and biologically active nonnatural compounds. The more or less simultaneous developments of mechanistically related variants, namely, the Kumada, Suzuki, Stille, Hiyama, and Negishi coupling reactions (Chapters 12, 2, 3, 4, and 15, respectively) of metallated alkenes and arenes with aryl and alkenyl halides or the metal-catalyzed formation and cycloisomerization of enynes have drawn profit from the improvement of and mechanistic insights into the Heck reaction. This, of course, applies vice versa as well. Using only a catalytic amount of a palladium(0) complex or a precursor to a palladium species, the Heck reaction can bring about unprecedented structural changes, particularly when conducted intramolecularly. The full potential of this palladium-catalyzed process is still being further explored as demonstrated by a total of over 7000 publications in the past 40 years by 1) The alkynylation of aryl and alkenyl halides, frequently also considered as Heck reactions, is described in Chapter 6.

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“…A typical procedure for the Heck reaction of aryl bromides with ethene [49] was used (Scheme 3-55): a 1-L glass autoclave was charged with a magnetic stimng bar as well as a mixture of 4'-bromobiphenyl-4-sulfonic acid (2-S03H) (172 g, 0.55 mol), sodium 3-(dipheny1phosphanyl)benzenesulfonate (3.78 g 10.4 mmol), and demineralized water (174 mL). The autoclave was cooled with ice-water, while triethylamine ( 189 mL, 1.36 mol) was added slowly with manual stirring until the solids had dissolved.…”

Section: Dipotassium (E)-44'-diphenylstilbene-4'4-disulfonate (Stilmentioning

confidence: 99%

“…The ratio between the styrene and stilbene formed depends on the excess of ethene, which can be controlled by the applied pressure (Scheme 3-2) [49]. Although Heck reactions with tetrasubstituted alkenes are known, their examples are rare (Scheme 3-3) [50-521.…”

mentioning

confidence: 99%

Palladium‐Catalyzed Coupling of Organyl Halides to Alkenes — the Heck Reaction

Bräse¹,

Meijere²

1998

Metal‐Catalyzed Cross‐Coupling Reactions

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About 25 years ago, a Japanese and an American group simultaneously designed and executed palladium-catalyzed coupling reactions of aryl and alkenyl halides with alkenes [ 11. In subsequent investigations, Richard Heck and his group demonstrated the usefulness and rather broad scope of this new catalytic transformation. The real push to utilize this powerful C-C bond-forming process, however, started only about 12 years ago; now, an impressive number of publications has established the so-called Heck reaction [2] as an indispensable method in organic synthesis [3]. The applications range from the preparation of hydrocarbons, novel polymers, and dyes to new advanced enantioselective syntheses of natural products. The simultaneous developments of mechanistically related variants, namely the Kumada, Suzuki, Stille, and Negishi coupling reactions (Chapters 1, 2, and 4 in this book, respectively) of metallated alkenes and arenes with alkenes or the metalcatalyzed formation and cycloisomerization of enynes have drawn profit from the improvement of and mechanistic insights into the Heck reaction. This, of course, applies conversely as well. Using only a catalytic amount of a palladium(0) complex, the Heck reaction can bring about unprecedented structural changes, particularly when conducted intramolecularly. Although the potential of this palladium-catalyzed process has not yet been at all fully explored, it is appropriate to say, even at this stage, that the Heck reaction is one of the true "power tools" in contemporary organic synthesis [4].In this chapter, an attempt is made to summarize the current state of understanding of the basics of the mechanism, to provide an overview over the diverse and sometimes mysterious compositions of applicable catalyst "cocktails", and to review important recent developments and applications of this reaction principle. Principles The MechanismEven at an early stage in the evolution of the Heck reaction into a facile method for the preparation of alkenyl-and aryl-substituted alkenes, reasonable concepts for the mechanism emerged, which could serve at least as working hypotheses. 99Metal-catalyzed Cross-coupling Reactions Edited by François Diederich, Peter J. Stang A coordinatively unsaturated 14-electron palladium(0) complex, usually coordinated with weak donor ligands (usually tertiary phosphanes), has meanwhile been proven to be the catalytically active species [5]. This complex is mostly generated in situ. Tetrakis(triphenyIphosphane)palladium(O) [6], which exists in an equilibrium with tris(triphenylphosphane)palladium(O) and free triphenylphosphane in solution, is frequently employed. The endergonic loss of a second phosphane ligand [7] leads to the catalytically active bis(triphenylphosphane)palladium(O). However, palladium(I1) complexes such as bis(tripheny1phosphane)palladium dichloride or palladium acetate, which are easily reduced (e.g. by triarylphosphanes; see below) in the reaction medium, are more commonly employed for convenience, as they are inherently stable towards ...

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A New Efficient Synthesis of the Stilbenoid Laser Dyes BPS and Stilbene I by Palladium‐Catalyzed Coupling of Ethene with Bromoarenes

Cited by 12 publications

References 0 publications

Development of the Traceless Phenylhydrazide Linker for Solid‐Phase Synthesis

Development of the Traceless Phenylhydrazide Linker for Solid‐Phase Synthesis

Cross‐Coupling of Organyl Halides with Alkenes – The Heck Reaction

Palladium‐Catalyzed Coupling of Organyl Halides to Alkenes — the Heck Reaction

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