Aerobic/Room-Temperature-Compatible s-Block Organometallic Chemistry in Neat Conditions: A Missing Synthetic Tool for the Selective Conversion of Nitriles into Asymmetric Alcohols

Highly-efficient and selective one-pot/two-step modular double addition of different highly polar organometallic reagents (RLi/RMgX) to nitriles en route to asymmetric tertiary alcohols (without the need for isolation/purification of any halfway reaction intermediate) has been studied, for the first...

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Detalles Bibliográficos
Autores: Elorriaga Muñoz, David, Parra Cadenas, Blanca, García Alvarez, Joaquín, Carrillo Hermosilla, Fernando, Antiñolo García, Antonio Fermín
Tipo de recurso: artículo
Fecha de publicación:2022
País:España
Institución:Universidad de Castilla-La Mancha
Repositorio:RUIdeRA. Repositorio Institucional de la UCLM
OAI Identifier:oai:ruidera.uclm.es:10578/41434
Acceso en línea:https://hdl.handle.net/10578/41434
Access Level:acceso abierto
Palabra clave:alcoholes asimétricos
nitrilos
Química inorgánica
Química organometálica
Descripción
Sumario:Highly-efficient and selective one-pot/two-step modular double addition of different highly polar organometallic reagents (RLi/RMgX) to nitriles en route to asymmetric tertiary alcohols (without the need for isolation/purification of any halfway reaction intermediate) has been studied, for the first time, in the absence of external/additional organic solvents (neat conditions), at room temperature and under air/moisture (no protecting atmosphere is required), which are generally forbidden reaction conditions in the field of highly-reactive organolithium/organomagnesium reagents. The one-pot modular tandem protocol demonstrated high chemoselectivity with a broad range of nitriles, as no side reactions (Li/halogen exchange, ortho-lithiations or benzylic metalations) were detected. Finally, this protocol could be scaled up, thus proving that this environmentally friendly methodology is amenable for a possible applied synthesis of asymmetric tertiary alcohols under bench type reaction conditions and in the absence of external organic solvents.