Solvent-free [Ru]-catalyzed isomerization of allyl glycidyl ether: The scope, effectiveness and recycling of catalysts, and exothermal effect

Urbala, Magdalena

doi:10.1016/j.apcata.2015.08.012

Cited by 6 publications

(14 citation statements)

References 45 publications

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“…This behaviour strongly depends on the structure of [Ru] pre-catalyst and also the structure of unsaturated substrate. For example, in the case of the most popular [RuCl 2 (PPh 3 ) 3 ] and olefin or alkyl allyl ethers as substrates, the peroxides act as very active catalyst activators [17,38], while in allyl glycidyl ether isomerization they significantly reduced reaction progress [18]. However, notwithstanding this, there is no doubt that AHP is one of the most important factors affecting the efficiency of [Ru] complexes.…”

Section: Resultsmentioning

confidence: 99%

“…We observed that the raising of reaction temperature only by 20 • C had a dramatic effect on the rate of the isomerization reaction, giving a rate enhancement of ca. 18 Table 3). However, performing the isomerization at the higher reaction temperature of 100 • C in the presence of Bu 3 N caused a substantial increase in the activity of this pre-catalyst with an almost complete conversion and selectivity to 1-propenyl derivative in 3 h (entry 6).…”

Section: Entrymentioning

confidence: 99%

“…The both fundamental and applied aspects of the isomerization of multi-functional alkyl allyl ethers to 1-propenyl derivatives catalyzed by ruthenium complexes [16][17][18][19][20][21], including the synthesis of high purified allyl substrates [22] and also the application of 1-propenyl ether monomers in the UV-curing polymeric systems [23][24][25] are the main focus of the research in our group (Scheme 1): Scheme 1. The strategy of the synthesis and application of 1-propenyl monomers.…”

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confidence: 99%

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Highly Productive Synthesis of 1-Propenyloxybutan-1-ol Under Solvent-Free Homogeneous Ruthenium Catalyst Conditions

Urbala

2020

Catalysts

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The 1-propenyl ethers bearing free hydroxyl groups of CH3CH=CH–O–A–OH type (hydroxyalkyl 1-propenyl ethers, 1-propenyloxyalcohols) are the most desired as the reactive diluents for photopolymerizable systems with enhanced reactivity or intermediates for the synthesis of hybrid monomers for special applications. The ruthenium complexes-catalyzed isomerization of allyl ethers under solvent-free conditions is an atom-economical and environmentally sustainable method for their production. Here, the reaction conditions and limitations for the highly productive and selective synthesis of model 4-(1-propenyloxy)butan-1-ol have been investigated. The minimal loading of ruthenium pre-catalysts needed for completion of reaction within reasonable times was priority assumption. It was found that [RuClH(CO)(PPh3)3] or [RuCl2(PPh3)3] exhibited extremely high catalytic activity under optimized non-oxidative reaction conditions. The key effect of reaction temperature on the activation pre-catalyst and the exothermal effects of isomerization was discovered. The practically quantitative yields of 4-(1-propenyloxy)butan-1-ol were achieved with using of very low loading of [Ru] (5 ppm) and Bu3N (to maintain reaction chemoselectivity) at the temperature of 120 °C for only 0.5 h. Consequently, the attained TON (turnover number) and TOF (turnover frequency) values of ca. 198,000 and 390,000 h−1 were unprecedentedly high and industrial attractive. On the other hand, the direct recycling of ruthenium catalyst is not a reasonable method for improving catalyst productivity.

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Section: Resultsmentioning

confidence: 99%

Section: Entrymentioning

confidence: 99%

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confidence: 99%

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Highly Productive Synthesis of 1-Propenyloxybutan-1-ol Under Solvent-Free Homogeneous Ruthenium Catalyst Conditions

Urbala

2020

Catalysts

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“…The isomerization reactions were conducted under solvent-free conditions and under the air or argon atmosphere using the Schlenk method according to the procedure described by us previously [12][13][14] . The allyl substrate (5 mmole) was placed into screw-capped glass ampoules together with ruthenium complex and stirred for given period time (the reaction conditions are given in footnotes of Table 1 and 2).…”

Section: The General Methodology Of Isomerization Reactionmentioning

confidence: 99%

“…This strategy with using readily available of allyl ethers of alcohols, diols and polyols from both natural and synthetic sources and [RuCl 2 (PPh 3 ) 3 ] was originally initiated and investigated by Crivello group 4 and postulated as easy and versatile method of synthesis of the UV-reactive mono-, di-and multifunctional 1-propenyl ether monomers. Our work in this area focused on wide and comprehensive studies of the reactions of multi-functional O-allyl systems with [Ru] complexes together with technological aspects of this processes [8][9][10][11][12][13][14] and also application of 1-propenyl ether monomers in UV curing polymeric systems 15-19 . The 1-propenyl ethers bearing free hydroxyl groups of CH 3 CH=CH-O-A-OH type (hydroxyalkyl 1-propenyl ethers, 1-propenyloxyalcohols) are the most desire as the reactive diluents for photopolymerizable systems with enhanced reactivity 15 or intermediates for the synthesis of hybrid monomers for special applications 1, 3 .…”

Section: Introductionmentioning

confidence: 99%

Technological aspects of synthesis of poly(ethylene glycol) mono-1-propenyl ether monomers

Urbala

2020

Polish Journal of Chemical Technology

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For the first time, the technological aspects of the highly productive and selective synthesis of UV-reactive poly(ethylene glycol) mono-1-propenyl ether monomers was developed. The solvent-free isomerization of model commercial available 2-allyloxyethanol and allyloxypoly(ethylene glycol) derivatives, type Allyl–[OCH2CH2]n–OH, n = 1–5, into a 1-propenyl derivative under the homogeneous catalysis conditions using the ruthenium complexes were evaluated. The effect of a various reaction conditions (i.e. the concentration of [Ru] complex, the reaction temperature, reaction gas atmosphere) together with trace amounts of allyl hydroperoxides formed via autoxidation reaction of allyl substrates on the productivity of catalyst was examined in detail. Moreover, the significant role of the allyl substrate structures on the catalytic activity of ruthenium catalysts were also recognized. The optimal parameters of the scaled-up synthesis together with productivity of catalyst were first established.

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Cobalt‐Catalyzed Chemoselective Isomerization of 2‐Substituted Allyl Ethers Induced by Hydrogen Atom Transfer

You

Qiu

et al. 2022

Asian J Org Chem

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A simple, mild and efficient method for the isomerization of 2‐substituted allyl ethers has been developed by cobalt‐catalyzed hydrogen atom transfer (HAT) process. The trivalent cobalt complex oxidized in‐situ by tert‐butyl hydroperoxide (tBuOOH) exhibits higher catalytic activity than prefabricated trivalent cobalt catalysts. This facile protocol displays excellent chemoselectivity, good functional group tolerance and high yields. The obtained vinyl ethers can be easily hydrolyzed by N‐iodosuccinimide/water to afford corresponding phenols or alcohols.

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Solvent-free [Ru]-catalyzed isomerization of allyl glycidyl ether: The scope, effectiveness and recycling of catalysts, and exothermal effect

Cited by 6 publications

References 45 publications

Highly Productive Synthesis of 1-Propenyloxybutan-1-ol Under Solvent-Free Homogeneous Ruthenium Catalyst Conditions

Highly Productive Synthesis of 1-Propenyloxybutan-1-ol Under Solvent-Free Homogeneous Ruthenium Catalyst Conditions

Technological aspects of synthesis of poly(ethylene glycol) mono-1-propenyl ether monomers

Cobalt‐Catalyzed Chemoselective Isomerization of 2‐Substituted Allyl Ethers Induced by Hydrogen Atom Transfer

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