Olefin Metathesis: From Academic Concepts to Commercial Catalysts

Czaban, Justyna; Torborg, C.; Grela, Karol

doi:10.1002/9781118354520.ch09

Cited by 8 publications

(1 citation statement)

References 252 publications

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“…α-Olefins are the most abundant petrochemical feedstock beyond alkanes . Despite their ubiquity and low cost, the use of α-olefins in the commercial manufacture of commodity chemicals is largely restricted to polymerization, hydroformylation, and alkene metathesis . The discovery of alternate classes of byproduct-free catalytic C–C couplings that convert α-olefins to value-added products remains an important yet elusive goal.…”

Section: Introductionmentioning

confidence: 99%

Osmium(0)-Catalyzed C–C Coupling of Ethylene and α-Olefins with Diols, Ketols, or Hydroxy Esters via Transfer Hydrogenation

et al. 2016

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Osmium(0) complexes derived from Os3(CO)12 and XPhos (2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl) catalyze the C-C coupling of α-hydroxy esters 1a-1i, α-ketols 1j-1o or 1,2-diols dihydro-1j-1o with ethylene 2a to form ethylated tertiary alcohols 3a-3o. As illustrated in couplings of 1-octene 2b with vicinally dioxygenated reactants 1a, 1b, 1i, 1j, 1k, 1m, higher α-olefins are converted to adducts 4a, 4b, 4i, 4j, 4k, 4m with complete levels of branched regioselectivity. Oxidation level independent C-C coupling is demonstrated by the reaction of 1-octene 2b with diol dihydro-1k, α-ketol 1k and dione dehydro-1k. Functionalized olefins 2c-2f react with ethyl mandelate 1a to furnish adducts 5a-8a as single regioisomers. The collective data, including deuterium labeling studies, are consistent with a catalytic mechanism involving olefin-dione oxidative coupling to form an oxa-osmacyclopentane, which upon reductive cleavage via hydrogen transfer from the secondary alcohol reactant releases the product of carbinol C-alkylation with regeneration of the ketone. Single crystal X-ray diffraction data of the dinuclear complex Os2(CO)4(O2CR)2(XPhos)2 and the trinuclear complex Os3(CO)11(XPhos) are reported. These studies suggest increased π-backbonding at the stage of the metal-olefin π-complex plays a critical role in facilitating alkene-carbonyl oxidative coupling, as isostructural ruthenium(0) complexes, which are weaker π-donors, do not catalyze the transformations reported herein.

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Section: Introductionmentioning

confidence: 99%

Osmium(0)-Catalyzed C–C Coupling of Ethylene and α-Olefins with Diols, Ketols, or Hydroxy Esters via Transfer Hydrogenation

et al. 2016

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Ring‐Closing Metathesis

Koning¹,

Otterlo²

2015

Arene Chemistry

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Low Catalyst Loadings in Self‐Metathesis of 1‐Dodecene

2013

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A series of ruthenium catalysts has been screened in the self-metathesis of 1-dodecene with and without the addition of benzoquinones. Many of these catalysts demonstrated excellent selectivity and yields with as low as 10 ppm catalyst loading. Reactions have been conducted under decreased pressure or under argon bubbling, which caused a tremendous increase in yield and selectivity of the examined process.Scheme 1. Possible reactions of linear alkenes in the presence of metathesis catalyst (PMP = primary metathesis products, IP = isomerization products, SMP = secondary metathesis products).Scheme 2. Self-metathesis of 1-dodecene. 1998

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Olefin Metathesis: From Academic Concepts to Commercial Catalysts

Cited by 8 publications

References 252 publications

Osmium(0)-Catalyzed C–C Coupling of Ethylene and α-Olefins with Diols, Ketols, or Hydroxy Esters via Transfer Hydrogenation

Osmium(0)-Catalyzed C–C Coupling of Ethylene and α-Olefins with Diols, Ketols, or Hydroxy Esters via Transfer Hydrogenation

Ring‐Closing Metathesis

Low Catalyst Loadings in Self‐Metathesis of 1‐Dodecene

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