Palladium-catalyzed vinylation of conjugated dienes

Patel, Babu A.; Kao, Lien-Chung; Cortese, Nicholas A.; Minkiewicz, J. V.; Heck, Richard F.

doi:10.1021/jo01320a005

Cited by 40 publications

(12 citation statements)

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“…[10] Among the diverse methods developed for the functionalization of 1,3dienes,c arboamination protocols remain scarce and are predominately limited to 1,2-difunctionalizations. [11,12] To the best of our knowledge there is no general method for the regio-and E-selective 1,4-carboamination of conjugated dienes available to date. [12] Inherently,t he selective 1,4-difunctionalization of conjugated dienes has several challenges.F irst, the addition of the nucleophile has to occur in ar egioselective manner to avoid the formation of regioisomers.Inaddition, the resulting allyl species has to undergo as elective reductive elimination to promote the desired transformation.…”

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“…[11,12] To the best of our knowledge there is no general method for the regio-and E-selective 1,4-carboamination of conjugated dienes available to date. [12] Inherently,t he selective 1,4-difunctionalization of conjugated dienes has several challenges.F irst, the addition of the nucleophile has to occur in ar egioselective manner to avoid the formation of regioisomers.Inaddition, the resulting allyl species has to undergo as elective reductive elimination to promote the desired transformation. Furthermore,i somerization processes that could result in the creation of conjugated products [13] and potential Heck-type reactivity via b-He limination need to be suppressed.…”

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Intermolecular 1,4‐Carboamination of Conjugated Dienes Enabled by Cp*Rh^III‐Catalyzed C−H Activation

et al. 2019

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Ap rotocol for the three-component 1,4-carboamination of dienes is described. Synthetically versatile Weinreb amides were coupled with 1,3-dienes and readily available dioxazolones as the nitrogen source using [Cp*RhCl 2 ] 2-catalyzedC À Ha ctivation to deliver the 1,4-carboaminated products.T his transformation proceeds under mild reaction conditions and affords the products with high levels of regioand E-selectivity.M echanistic investigations suggest an intermediate Rh III-allyl species is trapped by an electrophilic amidation reagent in ar edox-neutral fashion. Nitrogen-containing molecules are of fundamental importance to pharmaceutical science and can be found in av ast number of bioactive natural products. [1] Difunctionalizations,

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Intermolecular 1,4‐Carboamination of Conjugated Dienes Enabled by Cp*Rh^III‐Catalyzed C−H Activation

et al. 2019

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“…If the vinylic halide exists in isomeric forms, the oxidative addition occurs with complete retention of stereochemistry. Adding the vinylic palladium complex to the olefin occurs to place the organic group on the least-substituted olefinic carbon or on the more distant carbon if one is substituted with a strongly electron-withdrawing group (see Equations 5,6,and 7). The β-hydride elimination takes place largely or exclusively to form the conjugated diene π-complex.…”

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confidence: 99%

“…The last compound is only useful with aromatic or certain vinyl halides where mixtures of allylic amines would not be formed. A typical diene example is the reaction of vinyl bromide with butadiene and piperidine which gives E-N-(2,5-hexadienyl)-piperidine in 70% yield (7). The product of this reaction can be reacted again and used to extend the carbon chains by six atoms (see below).…”

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Palladium-Triarylphosphine Complexes as Catalysts for Vinylic Halide Reactions

Heck

1982

Advances in Chemistry

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Palladium acetate-triarylphosphine complexes catalyze the addition of vinylic groups from vinylic halides to olefinic compounds in the presence of amines. Conju gated dienes are major products from α,β-unsaturated acids, esters, or nitriles while unactivated olefinic com pounds react best in the presence of secondary amines where allylic amines are major products. The reactions are usually regio-and stereospecific. The synthetic util ity of the reaction is illustrated with a wide variety of examples. P alladium-triarylphosphine complexes are catalysts for the reac tion of aryl, heterocyclic, benzyl, and vinylic halides with olefins and amines (I). The usual catalyst is a combination of pal ladium^) acetate with two equivalents of a triarylphosphine. The complex that is formed is reduced in situ in the reaction mixtures to an active Pd(0) phosphine complex (see Equations 1, 2, 3, and 4 which depict catalyst formation). This species then oxidatively adds the or ganic halide (see Equation 2) and the adduct in turn adds to the olefinic reactant (see Equation 3). The organic group adds mainly or often exclusively to the less-substituted olefinic carbon. This addition product is generally unstable because sp 3 carbon-hydrogen bonds usually will be in positions beta to the palladium group, and /3-hydride elimination of the palladium hydride group will occur. The elimina tion produces olefin-π-complexes initially. After dissociation or dis placement of the hydridopalladium halide group from the π complex, the hydride decomposes into the Pd(0) phosphine complex and hy drogen halide. The hydrogen halide is neutralized by the amine pres ent. The Pd(0) complex then reacts with the organic halide again and the cycle is repeated.

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“…The formation of the product can be explained on the basis of the addition of the arylpalladium intermediate to the terminal double bond of the diene followed by the arrangement to the π-allylic complex and iodide ion−acetate ligand exchange. The final attack of the hydroxy group upon the complex with displacement of the palladium complex gives the cyclic acetal, while palladium catalyst oxidatively adds more aryl halide to start the catalytic cycle once more 4 Proposed Mechanism that Takes into Account the γ-Arylation of 1-(3-Hydropropoxy)buta-1,3-dienes …”

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Palladium-Catalyzed Heck Reaction on 1-Alkoxy-1,3-dienes: A Regioselective γ-Arylation of α,β-Unsaturated Carbonyl Compounds

2003

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[reaction: see text] alpha,beta-Unsaturated acetals afford, in the presence of the LIC-KOR superbase, 1-alkoxybuta-1,3-dienes. These substrates cross couple with aryl derivatives in the presence of Pd catalyst (Heck conditions) in a regio- and stereoselective mode. With dialkyl acetals, the reaction affords arylated dienes; on the other hand, in the case of 1,3-dioxane derivatives, the final outcome of the process formally corresponds to the direct gamma-arylation reaction of the starting alpha,beta-unsaturated material.

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Palladium-catalyzed vinylation of conjugated dienes

Cited by 40 publications

References 4 publications

Intermolecular 1,4‐Carboamination of Conjugated Dienes Enabled by Cp*Rh^III‐Catalyzed C−H Activation

Intermolecular 1,4‐Carboamination of Conjugated Dienes Enabled by Cp*Rh^III‐Catalyzed C−H Activation

Palladium-Triarylphosphine Complexes as Catalysts for Vinylic Halide Reactions

Palladium-Catalyzed Heck Reaction on 1-Alkoxy-1,3-dienes: A Regioselective γ-Arylation of α,β-Unsaturated Carbonyl Compounds

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Palladium-catalyzed vinylation of conjugated dienes

Cited by 40 publications

References 4 publications

Intermolecular 1,4‐Carboamination of Conjugated Dienes Enabled by Cp*RhIII‐Catalyzed C−H Activation

Intermolecular 1,4‐Carboamination of Conjugated Dienes Enabled by Cp*RhIII‐Catalyzed C−H Activation

Palladium-Triarylphosphine Complexes as Catalysts for Vinylic Halide Reactions

Palladium-Catalyzed Heck Reaction on 1-Alkoxy-1,3-dienes: A Regioselective γ-Arylation of α,β-Unsaturated Carbonyl Compounds

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Intermolecular 1,4‐Carboamination of Conjugated Dienes Enabled by Cp*Rh^III‐Catalyzed C−H Activation

Intermolecular 1,4‐Carboamination of Conjugated Dienes Enabled by Cp*Rh^III‐Catalyzed C−H Activation