1. Methyltriphenylphosphonium Methylcarbonate, an All-In-One Wittig Vinylation Reagent
- Author
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Lisa Cattelan, Marco Noè, Nicola Demitri, Alvise Perosa, Maurizio Selva, Cattelan, Lisa, Noè, Marco, Selva, Maurizio, Demitri, Nicola, and Perosa, Alvise
- Subjects
Green chemistry ,Models, Molecular ,General Chemical Engineering ,green chemistry ,halides ,phosphorus ,Wittig reactions ,ylides ,Molecular Conformation ,Alkenes ,chemistry.chemical_compound ,Onium Compounds ,Atom economy ,Environmental Chemistry ,Organic chemistry ,halide ,General Materials Science ,Reactivity (chemistry) ,Wittig reaction ,Triphenylphosphine ,chemistry.chemical_classification ,Trityl Compounds ,Settore CHIM/06 - Chimica Organica ,General Energy ,chemistry ,Ylide ,Reagent ,Hydrogen–deuterium exchange ,Indicators and Reagents ,phosphoru - Abstract
The methyltriphenylphosphonium methylcarbonate salt [Ph3 PCH3 ][CH3 OCO2 ], obtained directly by quaternarization of triphenylphosphine with dimethylcarbonate, is a latent ylide that promotes Wittig vinylation of aldehydes and ketones. Alkenes are obtained simply by mixing [Ph3 PCH3 ][CH3 OCO2 ] and the carbonyl and heating in a solvent (no base, no halides, and no inorganic byproducts). Deuterium exchange experiments and the particularly short anion-cation distance measured by XRD in [Ph3 PCH3 ][CH3 OCO2 ] allowed to explain the nature and reactivity of this species. Green chemistry metrics (atom economy, mass index, environmental factor) indicate that this vinylation procedure is more efficient than comparable ones. Deuterated [Ph3 PCD3 ][CH3 OCO2 ] promoted the synthesis of deuterated olefins.
- Published
- 2015