Stereodivergent Carbamate Synthesis by Selective In Situ Trapping of Organic Carbonate Intermediates
Trans-carbamate structures can be prepared in a diastereoselective approach by a judicious one-pot combination of in situ prepared organic carbonates and suitable amine reagents under appropriate reaction conditions. This unprecedented approach allows for stereo-divergence from a single oxirane subs...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2016 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:2072/356074 |
| Acceso en línea: | http://hdl.handle.net/2072/356074 https://doi.org/10.1002/chem.201504510 |
| Access Level: | acceso abierto |
| Palabra clave: | 54 |
| Sumario: | Trans-carbamate structures can be prepared in a diastereoselective approach by a judicious one-pot combination of in situ prepared organic carbonates and suitable amine reagents under appropriate reaction conditions. This unprecedented approach allows for stereo-divergence from a single oxirane substrate with easy access to both cis and trans carbamate isomers with high stereo- selectivity (dr > 19:1). Key to control the diastereo-selective nature of the conversions leading to the trans carbamates is the in situ formation of trans-configured oligo/polycarbonates through Al- catalysis providing the targeted products after aminolysis. The present results demonstrate the valorization of a renewable carbon-based reagent (CO2) into new valuable scaffolds and an unusual stereo- control exerted through carbonate intermediates. A series of control experiments support the proposed mechanistic rationale towards the trans-carbamate products which is based on the trapping of an in situ formed trans-configured oligo/polycarbonate. |
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