Direct Synthesis of Protected Arylacetaldehydes by Tetrakis(phosphane)palladium‐Catalyzed Arylation of Ethyleneglycol Vinyl Ether

Kondolff, Isabelle; Doucet, Henri; Santelli, Maurice

doi:10.1002/ejoc.200500540

Cited by 24 publications

(8 citation statements)

References 45 publications

(54 reference statements)

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“…For example, C -C bond formation between 38 and 39 occurred with high preference for the β-rather than α-position in 38 (38 → β-40). These findings were corroborated by Kang [52] and Sarpong [53]; Santelli also exploited the directing effect of a hydroxy group using an ethyleneglycol vinylether [54].…”

Section: Oxygen As a Directing Groupsupporting

confidence: 76%

“…Apart from this targeted design of nitrogen-based directing groups [23][24][25][26][41][42][43][44][45][46][47][48][49], suitably positioned hydroxy groups, as in allylic alcohols, have always been suspected to influence the regiochemical outcome of intermolecular Mizoroki-Heck reactions [50][51][52][53][54]. Heck himself was the first to propose coordination of a hydroxy oxygen to a palladium(II) atom, well aware of the relatively weak oxophilicity of palladium(II) [50].…”

Section: Oxygen As a Directing Groupmentioning

confidence: 98%

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Directed Mizoroki–Heck Reactions

Oestreich

2007

Topics in Organometallic Chemistry

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Section: Oxygen As a Directing Groupsupporting

confidence: 76%

Section: Oxygen As a Directing Groupmentioning

confidence: 98%

Directed Mizoroki–Heck Reactions

Oestreich

2007

Topics in Organometallic Chemistry

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“…A variety of phosphine ligands and solvent combinations were evaluated in a high-throughput setting using Pd(OAc) 2 and ethylene glycol vinyl ether. Curiously, the Tedicyp ligand, which was reported to favor the linear isomer, proved most efficient in our screening, affording the branched product 19 exclusively in 87–89% LC assay yield . Et 3 P was also effective, providing the desired product in 79–81% yield.…”

mentioning

confidence: 88%

“…Curiously, the Tedicyp ligand, which was reported to favor the linear isomer, proved most efficient in our screening, affording the branched product 19 exclusively in 87− 89% LC assay yield. 14 Et 3 P was also effective, providing the desired product in 79−81% yield. Ultimately, Et 3 P was selected for large scale application given its broader commercial availability (Scheme 4, step d).…”

mentioning

confidence: 98%

A Synthesis of a Spirocyclic Macrocyclic Protease Inhibitor for the Treatment of Hepatitis C

et al. 2016

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The development of a convergent and highly stereoselective synthesis of an HCV NS3/4a protease inhibitor possessing a unique spirocyclic and macrocyclic architecture is described. A late-stage spirocyclization strategy both enabled rapid structure-activity relationship studies in the drug discovery phase and simultaneously served as the basis for the large scale drug candidate preparation for clinical use. Also reported is the discovery of a novel InCl3-catalyzed carbonyl reduction with household aluminum foil or zinc powder as the terminal reductant.

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“…We have also reported several results for the Heck reaction using acrylates [51][52][53][54] and enol ethers. 55,56 Preliminary results of the reactions of alk-1-en-3-ones and aryl 57 or vinyl bromides 58 have also been reported. Here, we wish to report on the influence of the reaction conditions and on the scope and limitations of the reactions of a set of alk-1-en-3-one derivatives with electron-deficient, electron-excessive, and congested aryl bromides, as well as hetaryl bromides.…”

mentioning

confidence: 98%

Palladium-Catalysed Heck Reactions of Alk-1-en-3-ones with Aryl Bromides: A Very Simple Access to (E)-1-Arylalk-1-en-3-ones

Lemhadri¹,

Fall²,

Doucet³

et al. 2009

Synthesis

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When appropriate reaction conditions are used, very high yields of (E)-1-arylalk-1-en-3-one derivatives can be obtained by palladium-catalysed reactions of alk-1-en-3-ones with aryl bromides. The tetraphosphine cis,cis, cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane in combination with [Pd(C 3 H 5 )Cl] 2 was found to be a very efficient catalyst for this reaction. In general, higher reaction rates were observed with electron-poor aryl bromides, but the electron-rich aryl bromides 1-bromo-4-(dimethylamino)benzene and 4-bromoanisole also led to the arylated enones in high yields. Even with sterically very congested aryl bromides such as 9-bromoanthracene, 1-bromo-2,4,6-trimethylbenzene or 1-bromo-2,4,6-triisopropylbenzene, the expected (E)-1-arylalk-1-en-3-ones were obtained in moderate to good yields. These enones appear to be unstable under the reaction conditions, and the addition of a small amount of hydroquinone to the reaction mixture was found to be crucial, especially for the vinylation of electron-deficient aryl bromides. A variety of alk-1-en-3-ones has been employed, and better results in terms of substrate/ catalyst ratios were obtained when oct-1-en-3-one or hex-1-en-3-one was used than when but-1-en-3-one or pent-1-en-3-one was used. It should be noted that several reactions can be performed with as little as 0.1-0.001 mol% catalyst.The palladium-catalysed Heck vinylation is one of the most efficient methods for the formation of C-C bonds. [1][2][3][4] The reaction between aryl halides and alk-1-en-3-ones should give an economically and environmentally attractive access to 1-arylalk-1-en-3-one derivatives. In the literature, such reactions are generally performed with very reactive, but generally expensive, aryl iodides. 5-31 The use of aryl bromides would be more interesting both for environmental and economical reasons. In most cases, aryl bromides are cheaper than iodides, and with these substrates a lower mass of waste would be formed. However, so far, the Heck vinylation with alk-1-en-3-ones and aryl bromides, especially under low catalyst loading, has attracted less attention. 32,33 Moreover, surprisingly, most of the results were obtained using electron-neutral or electron-rich aryl bromides. For example, the reaction of 2-bromo-6-methoxynaphthalene with but-1-en-3-one in the presence of 2 mol% [PdCl 2 (PPh 3 ) 2 ] as catalyst gave the expected arylated enone in 45-92% yield. 32,33 The reaction of 2-bromo-1,4-dimethoxynaphthalene and but-1-en-3-one with 20 mol% tetrakis(triphenylphosphine)palladium led to the desired coupling product in 73% yield. 34 The reactions of bromobenzene, bromo(methoxy)benzenes, bromonaphthalenes, a bromophenylcarbohydrate, or a bromoindole with alk-1-en-3-ones in the presence of 10-20 mol% of a palladium(II) acetate/triphenylphosphine catalyst also gave the 1-aryl alk-1-en-3-ones in good yields. [35][36][37][38] On the other hand, in several other cases, moderate yields were obtained. The reaction of 2-bromotoluene or 1-bromo-2,4,5-trimethylbenzene with but...

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Direct Synthesis of Protected Arylacetaldehydes by Tetrakis(phosphane)palladium‐Catalyzed Arylation of Ethyleneglycol Vinyl Ether

Cited by 24 publications

References 45 publications

Directed Mizoroki–Heck Reactions

Directed Mizoroki–Heck Reactions

A Synthesis of a Spirocyclic Macrocyclic Protease Inhibitor for the Treatment of Hepatitis C

Palladium-Catalysed Heck Reactions of Alk-1-en-3-ones with Aryl Bromides: A Very Simple Access to (E)-1-Arylalk-1-en-3-ones

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