Palladium‐Catalysed Cross‐Coupling of Vinyldisiloxanes with Benzylic and Allylic Halides and Sulfonates

Frye, Elizabeth C.; Connor, Cornelius J. O’; Twigg, David G.; Elbert, Bryony L.; Laraia, Luca; Hulcoop, David G.; Venkitaraman, Ashok R.; Spring, David R.

doi:10.1002/chem.201200431

Cited by 24 publications

(25 citation statements)

References 63 publications

(42 reference statements)

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“…Vinyldisiloxanes 67 are adequate substrates for the palladium‐catalyzed cross‐coupling with allyl and benzyl chlorides or bromides 68 to afford the expected products 69 (Scheme ) 56…”

Section: Alkenylation Reactionsmentioning

confidence: 99%

The Hiyama Cross‐Coupling Reaction: New Discoveries

Foubelo

Nájera

Yus

2016

The Chemical Record

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ABSTRACT:In this review article recent developments in the Hiyama cross-coupling reaction from 2010 up today are presented. The most important methodology involves formation of biaryl systems by using aryl bromides or iodides and aryl trialkoxy silanes: other variants are far less studied. The most useful procedures are collected paying special attention to the synthetic application of this methodology in synthetic organic chemistry.

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“…Vinyldisiloxanes 67 are adequate substrates for the palladium‐catalyzed cross‐coupling with allyl and benzyl chlorides or bromides 68 to afford the expected products 69 (Scheme ) 56…”

Section: Alkenylation Reactionsmentioning

confidence: 99%

The Hiyama Cross‐Coupling Reaction: New Discoveries

Foubelo

Nájera

Yus

2016

The Chemical Record

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“…However, most of them involve aryl–alkyl cross‐couplings with allylic compounds as C

_{sp^{3}}

reagents . Several alkenylation or benzylation reactions were also reported but these methods often require pre‐generated stoichiometric organometallic compounds, which could limit the presence of functional groups in some cases . Oxidative alkenyl–benzyl cross‐couplings are another alternative but they always have some drawbacks such as high temperatures (>99 °C) and long reaction times (>10 h) .…”

Section: Optimization Of Reaction Conditionsmentioning

confidence: 99%

Cobalt‐Catalyzed Reductive Cross‐Coupling Between Styryl and Benzyl Halides

Cai

Benischke

Knöchel

et al. 2016

Chemistry A European J

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A simple and efficient protocol for the direct reductive cross-coupling between alkenyl and benzyl halides using a Co/Mn system has been developed. This reaction proceeds smoothly in the presence of [CoBr (PPh ) ] as the catalyst, with NaI as an additive in acetonitrile with a broad scope of functionalized alkenyl and benzyl halides. Different functional groups are tolerated on both coupling partners, thus, significantly extending the general scope of transition-metal-catalyzed benzylation of alkenyl halides. Moderate to excellent yields were also obtained. From a mechanistic point of view, a radical chain mechanism was proposed. This reaction is stereospecific and some studies suggest the retention of the double-bond configuration.

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“…The specific reactivity of 1,3-diphenylpropene is due to the presence of methylene group, being simultaneously in the allyl and benzyl positions. (E)-1,3-Diphenylpropene is usually obtained by treating a not easily accessible phenylacetaldehyde with a KOH alcohol solution [5,6], while the synthesis of less thermodynamically stable (Z)-isomer with an acceptable stereochemical purity is very problematic [7,8]. …”

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confidence: 99%

A Simple Synthesis of 1,3-Diphenylpropene

et al. 2018

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Abstract-A simple approach to the synthesis of 1,3-diphenylpropene isomers was developed based on Fe(acac) 3 -catalyzed cross-coupling of (E)-and (Z)-1,3-dichloropropenes with phenylmagnesium bromide.Keywords: 1,3-diphenylpropene, cross-coupling, Fe-catalyzed cross-coupling, Fe(acac) 3 ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 2, pp. 342-344. © Pleiades Publishing, Ltd., 2018. Original Russian Text © R.N. Shakhmaev, A.Sh. Sunagatullina, A.N. Vasilyeva, V.V. Zorin, 2018, published in Zhurnal Obshchei Khimii, 2018 1,3-Diphenylpropene isomers are used in organic synthesis as the starting substrates and model compounds [1][2][3][4]. The specific reactivity of 1,3-diphenylpropene is due to the presence of methylene group, being simultaneously in the allyl and benzyl positions. (E)-1,3-Diphenylpropene is usually obtained by treating a not easily accessible phenylacetaldehyde with a KOH alcohol solution [5,6], while the synthesis of less thermodynamically stable (Z)-isomer with an acceptable stereochemical purity is very problematic [7,8]. LETTERS TO THE EDITORWe investigated the possibility of obtaining 1,3-diphenylpropene 2 by Fe(acac) 3 -catalyzed crosscoupling of 1,3-dichloropropene 1 with phenylmagnesium bromide. It is known that available iron(III) salts are effective catalysts in cross-coupling reactions of Grignard reagents with vinyl [9--12] and allyl halides [13,14]. Fe(acac) 3 the most commonly used in the synthesis of natural compounds [15,16] and drugs [17][18][19][20] is advantageously characterized by low hygroscopicity, good solubility, and ease of handling [21].The reaction of (E)-1,3-dichloropropene la with 3 equiv of PhMgBr in tetrahydrofuran in the presence of 3 mol % of Fe(acac) 3 afforded a mixture of (E)-and (Z)-isomers of 1,3-diphenylpropene 2a and 2b (E : Z = 92 : 8) in a 52% yield. The introduction of the most frequently used ligands like N,N,N,N-tetramethylethylenediamine (TMEDA) [22] or N-methylpyrrolidone (NMP) [10], the replacement of THF by diethyl ether and the use of FeCl 3 as the catalyst did not substantially increase the yield of the reaction product. However, a decrease in the reaction temperature to -35°C results in an increase in the yield of 1,3-diphenylpropene to 80% with the same isomeric composition.The cross-coupling with (Z)-1,3-dichloropropene under similar conditions resulted in an isomeric mixture of 1,3-diphenylpropene (E : Z = 55 : 45) with 72% yield, while at room temperature the reaction direction shifted toward the formation of (E)-isomer (E : Z = 76 : 24). (E)-and (Z)-isomers of 1,3-diphenylpropene and diphenyl formed by homocoupling reaction were separated by column chromatography (Scheme 1).Structure and purity of the obtained compounds was confirmed by high-performance GLC analysis, NMR spectroscopy and chromato-mass spectrometry. A reliable evidence of the stereochemical configuration of isomers 2a and 2b was the values of spin-spin coupling constant of vinyl hydrogen atoms (J = 15.6 and 11.3 Hz), characteristic of the E-and Z-con...

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Palladium‐Catalysed Cross‐Coupling of Vinyldisiloxanes with Benzylic and Allylic Halides and Sulfonates

Cited by 24 publications

References 63 publications

The Hiyama Cross‐Coupling Reaction: New Discoveries

The Hiyama Cross‐Coupling Reaction: New Discoveries

Cobalt‐Catalyzed Reductive Cross‐Coupling Between Styryl and Benzyl Halides

A Simple Synthesis of 1,3-Diphenylpropene

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