Ruthenium catalysed regioselective synthesis of O-1-(1,3-dienyl) carbamates directly from CO2

Höfer, Jürgen; Doucet, Henri; Bruneau, Christian; Dixneuf, Pierre H.

doi:10.1016/0040-4039(91)80119-q

Cited by 39 publications

(18 citation statements)

References 10 publications

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“…O-1-(1,3-Dienyl) carbamates, with the Z isomer as the major product, were more efficiently obtained from 2-methyl-1-buten-3-yne, carbon dioxide, and a secondary amine in the presence of [Ru(methallyl) 2 (diphenylphosphanylethane)] as catalyst precursor (Scheme 5). [54] This carbamate synthesis avoids the use of phosgene derivatives and thus presents advantages over the classical route based on a carbamoyl chloride and an aldehyde enolate.…”

Section: Catalytic Synthesis Of Alkenyl Carbamates and Ureas: The Earmentioning

confidence: 99%

Metal Vinylidenes and Allenylidenes in Catalysis: Applications in Anti‐Markovnikov Additions to Terminal Alkynes and Alkene Metathesis

2006

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The involvement of a catalytic metal vinylidene species was proposed for the first time in 1986 to explain the regioselective formation of vinyl carbamates directly from terminal alkynes, carbon dioxide, and amines. Since this initial report, various metal vinylidenes and allenylidenes, which are key activation intermediates, have proved extremely useful for many alkyne transformations. They have contributed to the rational design of new catalytic reactions. This 20th anniversary is a suitable occasion to present the advancement of organometallic vinylidenes and allenylidenes in catalysis.

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Section: Catalytic Synthesis Of Alkenyl Carbamates and Ureas: The Earmentioning

confidence: 99%

Metal Vinylidenes and Allenylidenes in Catalysis: Applications in Anti‐Markovnikov Additions to Terminal Alkynes and Alkene Metathesis

2006

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“…[12,13] Interestingly, 2-methyl-1-buten-3-yne (24) could be used as a substrate, reacting with morpholine to give diene products that are activated Diels-Alder reaction partners (equation 3). [14] 2.2. Carboxylic Acid Nucleophiles 2.2.1 Intermolecular Reactions-Contemporaneous with his work on vinylcarbamate formation, Dixneuf disclosed the use of carboxylic acid nucleophiles to capture metal vinylidenes in a catalytic synthesis of enol esters.…”

Section: Carbamate Nucleophilesmentioning

confidence: 99%

Metal Vinylidenes as Catalytic Species in Organic Reactions

Trost

McClory

2008

Chemistry An Asian Journal

189

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Organic vinylidene species have found limited use in organic synthesis due to their inaccessibility. In contrast, metal vinylidenes are much more stable, and may be readily accessed through transition metal activation of terminal alkynes. These electrophilic species may be trapped by a number of nucleophiles. Additionally, metal vinylidenes can participate in pericyclic reactions and processes involving migration of a metal ligand to the vinylidene species. This review addresses the reactions and applications of metal vinylidenes in organic synthesis.

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“…1) ð1Þ C. Bruneau and J. Höfer showed that the catalytic addition of ammonium carbamate to isopropenylacetylene led to the regioselective synthesis of Z [ E O-1-(1,3-dienyl)carbamates (Eq. 2) [19]. For this reaction the best ruthenium(II) catalysts were of the type Ru(methallyl) 2 (Ph 2 P(CH 2 ) n PPh 2 ).…”

Section: Ruthenium-catalyzed Synthesis Of Vinyl-carbamatesmentioning

confidence: 99%

Early Steps of Homogeneous Catalysis in Rennes: Carbon Dioxide Incorporation, Alkyne Activation and Ruthenium Catalysis

Dixneuf

2014

Catal Lett

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This review reports the first discoveries in homogeneous catalysis in Rennes. Ruthenium(II) catalysts are shown to promote the activation of terminal alkynes and the synthesis of vinylcarbamates on addition of CO 2 and amines. The ruthenium-vinylidene are the key catalytic species. Applications to the addition of carboxylic acids to alkynes have opened the access to various enolesters and dienylesters via controlled catalyzed Markovnikov or anti-Markonikov additions. The catalytic synthesis of a-methylene cyclic carbonates and oxazolidinones from propargylic alcohols and CO 2 is presented and shown to lead to allene derivatives via palladium catalysis. Cp*RuX(COD) catalyst promote the head to tail oxidative couplings of alkene with alkyne, and the synthesis of functional dienes via 1,4 addition of H-nucleophiles to the biscarbene-ruthenium intermediate arising from head to head couplings of alkynes, whereas Cp*RuL 2 ? catalysts favour activation of alkynes via vinylidene intermediate.

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Ruthenium catalysed regioselective synthesis of O-1-(1,3-dienyl) carbamates directly from CO2

Cited by 39 publications

References 10 publications

Metal Vinylidenes and Allenylidenes in Catalysis: Applications in Anti‐Markovnikov Additions to Terminal Alkynes and Alkene Metathesis

Metal Vinylidenes and Allenylidenes in Catalysis: Applications in Anti‐Markovnikov Additions to Terminal Alkynes and Alkene Metathesis

Metal Vinylidenes as Catalytic Species in Organic Reactions

Early Steps of Homogeneous Catalysis in Rennes: Carbon Dioxide Incorporation, Alkyne Activation and Ruthenium Catalysis

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