Tetraphosphine/palladium-catalyzed Heck reactions of aryl halides with disubstituted alkenes

Kondolff, Isabelle; Doucet, Henri; Santelli, Maurice

doi:10.1016/j.tetlet.2003.09.092

Cited by 74 publications

(32 citation statements)

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“…We have already reported some results obtained in allylic substitution [24], for Suzuki cross-coupling [25] and for Sonogashira reaction [26] using this tedicyp/palladium catalyst. We have also reported several results obtained for Heck reaction [27][28][29][30][31][32][33][34][35]. We herein report on the reaction of aryl and heteroaryl bromides with 3,3-diacetoxypropene.…”

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confidence: 79%

Direct synthesis of cinnamaldehyde derivatives by reaction of aryl bromides with 3,3-diacetoxypropene catalyzed by a palladium–tetraphosphine complex

2005

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The tetraphosphine all-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane in combination with [Pd(C 3 H 5 )Cl] 2 affords an efficient catalyst for the synthesis of cinnamaldehyde derivatives by reaction of aryl bromides with 3,3-diacetoxypropene. The reaction gave directly the cinnamaldehyde derivatives very selectively. The coupling reaction of heteroaryl bromides or sterically congested aryl bromides such as 2,4,6-trimethylbromobenzene also proceeds.Cinnamaldehyde derivatives bearing various substituents on the aromatic ring are useful precursors for synthetic organic chemist. Palladium-catalyzed Heck reaction is one of the most powerful method for the formation of C-C bonds [1][2][3][4][5][6][7]. However, the synthesis of cinnamaldehyde derivatives by coupling of aryl bromides and acrolein is difficult due to the low stability and the low boiling point of acrolein. Most of the reaction described with acrolein were performed using reactive but expensive aryl iodides [8][9][10][11][12]. Few results have been described with less reactive aryl bromides [13]. Some examples of synthesis of cinnamaldehyde derivatives using the protected acrolein: acrolein diethylacetal have also been described [14]. With this substrate the reactions proceed in good yields with a variety of aryl bromides and iodides. These reactions were performed using Pd(OAc) 2 (3%), K 2 CO 3 (1.5 equiv.), KCl (1 equiv.), n Bu 4 NOAc (2 equiv.) as reaction mixture. However, the reactions performed with acrolein diethylacetal in the presence of a palladium/phosphine ligand catalyst led to mixtures of cinnamaldehyde derivatives and 3-arylpropionic esters. Palladium catalysts bearing ligands are often more efficient than ''ligand free'' palladium catalysts for Heck reaction using aryl bromides [15][16][17][18][19][20][21][22][23]. In order to obtain selectively cinnamaldehyde derivatives with catalysts bearing phosphine ligands we have studied this reaction in the presence of 3,3-diacetoxypropene. To our knowledge, the selectivity of Heck reaction with 3,3-diacetoxypropene has never been described. We studied this reaction using the thermally stable all-cis-1,2,3,4-tetrakis (diphenylphosphinomethyl)cyclopentane or tedicyp [24]/ palladium catalyst (figure 1). We have already reported some results obtained in allylic substitution [24], for Suzuki cross-coupling [25] and for Sonogashira reaction [26] using this tedicyp/palladium catalyst. We have also reported several results obtained for Heck reaction [27][28][29][30][31][32][33][34][35]. We herein report on the reaction of aryl and heteroaryl bromides with 3,3-diacetoxypropene.For this study, based on our previous results [27], DMF was chosen as the solvent. The reactions were performed at 130°C, under argon, in the presence of a ratio 1/2 of [Pd(C 3 H 5 )Cl] 2 /tedicyp as catalyst. 3,3-Diacetoxypropene was prepared on a large scale by addition of 3 mol% of FeCl 3 .6H 2 O to a mixture of acrolein (1 equiv.) and acetic anhydride (3 equiv.) at 0°C [36].First, we studied the reaction of 4-tbutylbrom...

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confidence: 79%

Direct synthesis of cinnamaldehyde derivatives by reaction of aryl bromides with 3,3-diacetoxypropene catalyzed by a palladium–tetraphosphine complex

2005

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“…The TONs drop rapidly when using less activated electrophiles. [181] Other applications of 51 concern the Heck coupling of b-bromostyrene (TONs > 10 4 with acrylates), [182] and the Sonogashira coupling using Cu as co-catalyst (TON > 10 6 in the coupling of iodobenzene with phenylacetylene). [183] Another new tetradentate P-based ligand is ferrocenyl-tetraphosphane 57.…”

Section: ð11þmentioning

confidence: 99%

High‐Turnover Palladium Catalysts in Cross‐Coupling and Heck Chemistry: A Critical Overview

2004

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This review discusses the problems associated with developing high-turnover catalysts for the cross-coupling and Heck reactions. New developments in the area, principally constituted by palladacycles and coordinatively unsaturated Pd catalysts featuring bulky phosphanes of high donicity, are reviewed from a mechanistic and synthetic standpoint, and compared with more traditional catalysts obtained from conventional mono-and polydentate Nand P-based ligands, as well as Pd catalysts without strong ligands, such as Pd colloids or heterogeneous catalysts. Carbene ligands are also briefly presented. Whereas a single, most promising approach to highturnover Pd catalysis cannot presently be defined, it is clear that the new "PdL 1 " catalysts (where L 1 is a monodentate bulky P ligand of high donicity) represent the latest, most important development in Pd research, certainly from the standpoint of scope and probably also from the standpoint of efficiency. High turnovers with these catalysts have been described and their use will certainly increase in the next few years. The review ends with a brief discussion containing practical considerations on how to choose a high TON catalyst for a given Heck or cross-coupling reaction of interest.

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“…Stereocontrol during the synthesis of highly substituted double bonds is a significant challenge in organic synthesis, 2 and the Heck reaction remains an important alternative. In this context, some examples of regio and stereoselective syntheses of trisubstituted α,β-unsaturated compounds, such as nitriles, 3,4 cinnamates [5][6][7][8][9][10] and aldehydes, 11 through either monoarylation of disubstituted olefins or direct diarylation of monosubstituted olefins, have been reported. Arylation of disubstituted alkenes without an electron-withdrawing group conjugated to the C=C double bond (e.g., α-or β-methylstyrene, 10,12 1,1-diphenylethene and transstilbene) [13][14][15] has also been investigated.…”

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confidence: 99%

Pd-catalyzed Heck reactions of aryl bromides with 1,2-diarylethenes

Limberger¹,

Poersch²,

Monteiro³

2011

J. Braz. Chem. Soc.

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Um sistema catalítico composto por Pd(OAc) 2 e P(o-tol) 3 foi aplicado na reação de Heck entre brometos de arila e diariletenos. Utilizando-se K 2 CO 3 como base e DMF como solvente, olefinas triarilsubstituídas foram obtidas com rendimentos de bons a excelentes. Brometos de arila com substituintes eletroretiradores foram menos ativos para a reação de acoplamento Heck e levaram à formação de produto de homoacoplamento em quantidades substanciais, indicando que a adição oxidativa não deve ser a etapa lenta da reação. A presença de substituintes no diarileteno afetou drasticamente a seletividade da reação. Realizou-se também a dupla arilação do estireno, levando diretamente à olefina triarilsubstituída, com rendimento de 73%.A catalytic system composed of Pd(OAc) 2 and P(o-tol) 3 was found to be effective for the Heck reaction of aryl bromides with diarylethylenes. Using K 2 CO 3 as a base and DMF as a solvent, trisubstituted olefins were obtained in good to excellent yields. Aryl bromides containing an electron-withdrawing group in para position were less reactive for the Heck coupling reaction and gave substantial amount of homocoupling by-product suggesting that oxidative addition is not the rate-determining step. Electron withdrawing group substituent in the para position of stilbene affects the regioselectivity of the reaction. In this case, the phenyl group from the Ph-Pd complex migrates preferentially to the same carbon of the double bond to which the phenyl is bonded. Finally, a one pot sequential double Heck arylation of styrene was performed, giving trisubstituted olefin with an overall yield of 73%.Keywords: Heck reaction, palladium, trisubstituted olefins, double arylation IntroductionPalladium-catalyzed Heck cross-coupling reactions are one of the most efficient methods for the construction of C−C bonds and have found widespread use in organic synthesis.1 Most Heck reactions involves arylation of monosubstituted alkenes (especially acrylates and styrene derivatives) to allow synthesis of disubstituted olefins with regio and stereoselective control. In contrast, fewer studies have been conducted on the arylation of disubstituted olefins or double arylation of mono-substituted olefins, to yield trisubstituted products. Stereocontrol during the synthesis of highly substituted double bonds is a significant challenge in organic synthesis, 2 and the Heck reaction remains an important alternative. In this context, some examples of regio and stereoselective syntheses of trisubstituted α,β-unsaturated compounds, such as nitriles, 3,4 cinnamates 5-10 and aldehydes, 11 through either monoarylation of disubstituted olefins or direct diarylation of monosubstituted olefins, have been reported. Arylation of disubstituted alkenes without an electron-withdrawing group conjugated to the C=C double bond (e.g., α-or β-methylstyrene, 10,12 1,1-diphenylethene and transstilbene)13-15 has also been investigated. However, to the best of our knowledge, no example using substituted stilbenes has been described. Recently, we re...

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Tetraphosphine/palladium-catalyzed Heck reactions of aryl halides with disubstituted alkenes

Cited by 74 publications

References 27 publications

Direct synthesis of cinnamaldehyde derivatives by reaction of aryl bromides with 3,3-diacetoxypropene catalyzed by a palladium–tetraphosphine complex

Direct synthesis of cinnamaldehyde derivatives by reaction of aryl bromides with 3,3-diacetoxypropene catalyzed by a palladium–tetraphosphine complex

High‐Turnover Palladium Catalysts in Cross‐Coupling and Heck Chemistry: A Critical Overview

Pd-catalyzed Heck reactions of aryl bromides with 1,2-diarylethenes

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