The Value and Application of Transition Metal Catalyzed Alkene Isomerization in Industry

Larsen, Casey R.; Grotjahn, Douglas B.

doi:10.1002/9783527651733.ch25

Cited by 34 publications

(43 citation statements)

References 73 publications

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“…(Figure 1b). Generally, it is well-known from the literature that the double-bond migration of alkenes [6,8,34] and allyl ether [7,16] catalyzed by [RuClH(CO)(PPh 3 ) 3 ] and other hydride ruthenium catalysts dominantly runs via the hydride addition-elimination mechanism with the preferential kinetic controlled Z isomer formation. Simultaneously the hydride ruthenium complexes are active catalyst in the Z-E or E-Z isomerization, accompanied the double bond migration [7,8].…”

Section: Entrymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…The isomerization of alkenes and their derivatives catalysed by TMCs is well-recognised in academic and industrial organic chemistry [6][7][8]. It is an elegant, green, clean, 100% atom-economic, one-pot, and one-step, efficient and environmentally sustainable way to valuable products, often without producing any by-products and without requiring toxic reagents.…”

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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: Entrymentioning

confidence: 99%

Section: Introductionmentioning

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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“…Olefins are essential intermediates and products in the fragrance, commodity chemicals, and pharmaceutical industries. [1][2][3] Positional isomerization of double bonds offers a highly attractive route to internal olefins, given the wide availability of terminal olefins and the perfect atom economy of double bond transposition. [4][5][6][7][8] However, preparing specific isomers with high stereo-and regioselectivity remains a major challenge in catalyst design.…”

Section: Introductionmentioning

confidence: 99%

Selecting Double Bond Positions with a Single Cation- Responsive Iridium Olefin Isomerization Catalyst

Camp¹,

Kita²,

Blackburn³

et al. 2020

Preprint

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<div><div><div><p>The catalytic transposition of double bonds holds promise as an ideal route to alkenes with value as fragrances, commodity chemicals, and pharmaceuticals; yet, selective access to specific isomers is a challenge, requiring independent development of different catalysts for different products. In this work, a single cation-responsive iridium catalyst is developed for the selective production of either of two different internal alkene isomers. In the absence of salts, a single positional isomerization of 1-butene derivatives furnishes 2-alkenes with exceptional regioselectivity and stereoselectivity. The same catalyst, in the presence of Na+, mediates two positional isomerizations to produce 3-alkenes. The synthesis of new iridium pincer-crown ether catalysts based on an aza-18-crown-6 ether proved instrumental in achieving cation-controlled selectivity. Experimental and computational studies guided the development of a mechanistic model that explains the observed selectivity for various functionalized 1-butenes, providing insight into strategies for catalyst development based on non-covalent modifications.</p></div></div></div>

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“…Mechanistic and spectroscopic studies revealed the in situ generation of a catalytically active nickel-hydride species triggered by oxidative addition of the phosphine oxide. The reaction is amenable to regioconvergent isomerization as well as β-selective remote hydrophosphination when stoichiometric secondary phosphine oxide/base were employed.The transposition of carbon-carbon double bonds 1,2 is arguably one of the most convenient approaches to convert an easily available olefin to another unsaturated molecule of interest, and has vast applications in various chemical industries 3,4 . Combining olefin isomerization with another functionalization reaction enables functional groups to be precisely incorporated at positions remote from the initial reaction site 1,5-8 .…”

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confidence: 99%

Secondary Phosphine Oxide-Activated Nickel Catalysts for Site-Selective Alkene Isomerization and Remote Hydrophosphination

Huang

Lim

Koh

2021

Preprint

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Catalytic systems that are readily modifiable to achieve olefin migration or remote functionalization are highly sought-after in chemical synthesis. Here, we show that the combination of a commercially available nickel(II) pre-catalyst and a secondary phosphine oxide ligand enables site- and stereoselective alkene transposition for up to nine double-bond migrations within terminal and internal olefins under mild reductive conditions. Substrates bearing diverse functionalities including Brønsted acidic and reducible carbonyl groups are tolerated. Mechanistic and spectroscopic studies revealed the in situ generation of a catalytically active nickel-hydride species triggered by oxidative addition of the phosphine oxide. The reaction is amenable to regioconvergent isomerization as well as β-selective remote hydrophosphination when stoichiometric secondary phosphine oxide/base were employed.

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The Value and Application of Transition Metal Catalyzed Alkene Isomerization in Industry

Cited by 34 publications

References 73 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

Selecting Double Bond Positions with a Single Cation- Responsive Iridium Olefin Isomerization Catalyst

Secondary Phosphine Oxide-Activated Nickel Catalysts for Site-Selective Alkene Isomerization and Remote Hydrophosphination

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