Highly Chemo-Selective Catalytic Coupling of Substituted Oxetanes and Carbon Dioxide

The chemo-selective coupling of oxetanes and carbon dioxide to afford functional, heterocyclic organic compounds known as six-membered cyclic carbonates remains a challenging topic. Here we describe an effective method for their synthesis relying on the use of Al-catalysis. The catalytic reactions c...

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Detalhes bibliográficos
Autores: Rintjema, Jeroen, Guo, Wusheng, Martin, Eddy, Escudero-Adán, Eduardo C., Kleij, Arjan W.
Tipo de documento: artigo
Estado:Versión aceptada para publicación
Data de publicação:2015
País:España
Recursos:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositório:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/356073
Acesso em linha:http://hdl.handle.net/2072/356073
https://doi.org/10.1002/chem.201501576
Access Level:Acceso aberto
Palavra-chave:54
Descrição
Resumo:The chemo-selective coupling of oxetanes and carbon dioxide to afford functional, heterocyclic organic compounds known as six-membered cyclic carbonates remains a challenging topic. Here we describe an effective method for their synthesis relying on the use of Al-catalysis. The catalytic reactions can be carried out with excellent selectivity for the cyclic carbonate product tolerating various (functional) groups present in the 2- and 3-position(s) of the oxetane ring, and the presented methodology is the first general approach towards the formation of six-membered cyclic carbonates (6MCCs) through oxetane/CO2 coupling chemistry. Apart from a series of substituted six-membered cyclic carbonates, also the unprecedented room temperature coupling of oxetanes and CO2 is disclosed giving, depending on the structural features of the substrate, a variety of five- and six-membered heterocyclic products. A mechanistic rationale is presented for their formation and support for the intermediary presence of a carbonic acid derivative is given. The presented functional carbonates may hold great promise as building blocks in organic synthesis and the development of new, biodegradable polymers.