Homo‐ and Cross‐Olefin Metathesis Coupling of Vinylphosphane Oxides and Electron‐Poor Alkenes: Access to P‐Stereogenic Dienophiles

Vinokurov, N. A.; Michrowska, Anna; Szmigielska, Anna; Drzazga, Zbigniew; Wójciuk, Grzegorz; Demchuk, Oleg M.; Grela, Karol; Pietrusiewicz, K. Michał; Butenschön, Holger

doi:10.1002/adsc.200505463

Cited by 50 publications

(26 citation statements)

References 90 publications

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“…[29] Gouvernour and Grela have simultaneously reported a successful CM of vinyl phosphine partners catalysed by Gru-II. [30] However, while the latter initiator was found to be ineffective in the more challenging self-CM of vinyl phosphane oxides, [31] this transformation was accomplished with the phosphane-free complex Gre-II. [31] Contrary to some previous reports, [32] we have discovered that CM of vinyl sulfones can also be effectively Scheme 4.…”

Section: Straightforward Enyne Cycloisomerisationmentioning

confidence: 99%

In an Attempt to Provide a User's Guide to the Galaxy of Benzylidene, Alkoxybenzylidene, and Indenylidene Ruthenium Olefin Metathesis Catalysts

Bieniek

Michrowska

Usanov

et al. 2008

Chemistry A European J

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220

158

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The data reported in this paper demonstrate that great care must be taken when choosing an appropriate catalyst for a given metathesis reaction. First-generation catalysts were found to be useful in the metathesis of sterically unhindered substrates. Second-generation catalysts (under optimised conditions) showed good to excellent activities toward sterically hindered and electron-withdrawing group (EWG)-substituted alkenes that do not react using the first-generation complexes. A strong temperature effect was noted on all of the reactions tested. Interestingly, attempts to force a reaction by increasing the catalyst loading were much less effective. Therefore, when possible, it is suggested that metathesis transformations should be carried out with a second-generation catalyst at 70 degrees C in toluene. However, different second-generation catalysts proved to be optimal for different applications and no single catalyst outperformed all others in all cases. Nevertheless, some empirical rules can be deduced from the model experiments, providing preliminary hints for the selection of the optimal catalysts.

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Section: Straightforward Enyne Cycloisomerisationmentioning

confidence: 99%

In an Attempt to Provide a User's Guide to the Galaxy of Benzylidene, Alkoxybenzylidene, and Indenylidene Ruthenium Olefin Metathesis Catalysts

Bieniek

Michrowska

Usanov

et al. 2008

Chemistry A European J

Self Cite

220

158

View full text Add to dashboard Cite

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“…However, these methods suffer from lack of stereoselectivity, limited substrate scope and the use of relatively drastic conditions that were not compatible with sensitive functional groups etc. 74 Hence, decarboxylative C-P bond formation can address an efficient alternative protocol to overcome these drawbacks. Cinnamic acids and alkyne acids were subjected to decarboxylative C-P bond formation for the first time.…”

Section: C-p Bond Formationmentioning

confidence: 99%

Decarboxylative functionalization of cinnamic acids

Borah

Yan

2015

Org. Biomol. Chem.

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Decarboxylative functionalization of α,β-unsaturated carboxylic acids is an emerging area that has been developed significantly in recent years. This critical review focuses on the different decarboxylative functionalization reactions of cinnamic acids leading to the formation of various C-C and C-heteroatom bonds. Apart from metal carboxylates, decarboxylation in cinnamic acids has been achieved efficiently under metal-free conditions, particularly via the use of hypervalent iodine reagents. We believe this review will encourage organic chemists to develop vinylic decarboxylation in a more appealing way with an understanding of new mechanistic insight.

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“…The behavior of differently substituted acrylates as substrates for the cross‐metathesis with ethyl sorbate showed the same correlations that were reported previously . A larger carboxylic group substituent decreased the reaction rate of the metathesis by making it more difficult for the molecules to reach the Ru active site . As seen in Table , the smaller the substituent of the acrylate, the higher the conversion to the cross‐metathesis product.…”

Section: Resultsmentioning

confidence: 99%

“…[48] Al arger carboxylic group substituent de-creasedt he reaction rate of the metathesis by making it more difficult for the molecules to reacht he Ru active site. [49] As seen in Table 3, the smaller the substituent of the acrylate, the higher the conversion to the cross-metathesis product. Moreover,u pon using fumarate as ar eactant ( Table 3, entry 5), the reactivity for cross-metathesisw as furtherd iminished owing to steric hindrance and the highstability of the diester.…”

Section: Reactantsubstituent Effectsmentioning

confidence: 99%

Bioderived Muconates by Cross‐Metathesis and Their Conversion into Terephthalates

et al. 2018

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Polyethylene terephthalate that is 100 % bioderived is in high demand in the market guided by the ever-more exigent sustainability regulations with the challenge of producing renewable terephthalic acid remaining. Renewable terephthalic acid or its precursors can be obtained by Diels-Alder cycloaddition and further dehydrogenation of biomass-derived muconic acid. The cis,cis isomer of the dicarboxylic acid is typically synthesized by fermentation with genetically modified microorganisms, a process that requires complex separations to obtain a high yield of the pure product. Furthermore, the cis isomer has to be transformed into the trans,trans form and has to be esterified before it is suitable for terephthalate synthesis. To overcome these challenges, we investigated the synthesis of dialkyl muconates by cross-metathesis. The Ru-catalyzed cross-coupling of sorbates with acrylates, which can be bioderived, proceeded selectively to yield diester muconates in up to 41 % yield by using very low catalyst amounts (0.5-3.0 mol %) and no solvent. In the optimized procedure, the muconate precipitated as a solid and was easily recovered from the reaction medium. Analysis by GC-MS and NMR spectroscopy showed that this method delivered exclusively the trans,trans isomer of dimethyl muconate. The Diels-Alder reaction of dimethyl muconate with ethylene was studied in various solvents to obtain 1,4-bis(carbomethoxy)cyclohexene. The cycloaddition proceeded with very high conversions (77-100 %) and yields (70-98 %) in all of the solvents investigated, and methanol and tetrahydrofuran were the best choices. Next, the aromatization of 1,4-bis(carbomethoxy)cyclohexene to dimethyl terephthalate over a Pd/C catalyst resulted in up to 70 % yield in tetrahydrofuran under an air atmosphere. Owing to the high yield of the reaction of dimethyl muconate to 1,4-bis(carbomethoxy)cyclohexene, no separation step was needed before the aromatization. This is the first time that cross-metathesis is used to produce bioderived trans,trans-muconates as precursors to renewable terephthalates, important building blocks in the polymer industry.

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Homo‐ and Cross‐Olefin Metathesis Coupling of Vinylphosphane Oxides and Electron‐Poor Alkenes: Access to P‐Stereogenic Dienophiles

Cited by 50 publications

References 90 publications

In an Attempt to Provide a User's Guide to the Galaxy of Benzylidene, Alkoxybenzylidene, and Indenylidene Ruthenium Olefin Metathesis Catalysts

In an Attempt to Provide a User's Guide to the Galaxy of Benzylidene, Alkoxybenzylidene, and Indenylidene Ruthenium Olefin Metathesis Catalysts

Decarboxylative functionalization of cinnamic acids

Bioderived Muconates by Cross‐Metathesis and Their Conversion into Terephthalates

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