Enantioselective Organocatalytic Diels–Alder Trapping of Photochemically Generated Hydroxy-o-Quinodimethanes
The photoenolization/Diels–Alder strategy offers straightforward access to synthetically valuable benzannulated carbocyclic products. This historical light-triggered process has never before succumbed to efforts to develop an enantioselec- tive catalytic approach. Herein, we demonstrate how asym- me...
| 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:2072/350685 |
| Acceso en línea: | http://hdl.handle.net/2072/350685 https://doi.org/10.1002/anie.201509472 |
| Access Level: | acceso abierto |
| Palabra clave: | 54 |
| Sumario: | The photoenolization/Diels–Alder strategy offers straightforward access to synthetically valuable benzannulated carbocyclic products. This historical light-triggered process has never before succumbed to efforts to develop an enantioselec- tive catalytic approach. Herein, we demonstrate how asym- metric organocatalysis provides simple yet effective catalytic tools to intercept photochemically generated hydroxy-o-qui- nodimethanes with high stereoselectivity. We used a chiral organic catalyst, derived from natural cinchona alkaloids, to activate maleimides toward highly stereoselective Diels–Alder reactions. An unconventional mechanism of stereocontrol is operative, wherein the organocatalyst is actively involved in both the photochemical pathway, by leveraging the formation of the reactive photoenol, and the stereoselectivity-defining event. |
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