2026-04-14T07:11:39Zhttps://recercat.cat/oai/request

oai:recercat.cat:2072/3506852024-12-20T19:19:16Zcom_2072_300912com_2072_4427col_2072_301309

Enantioselective Organocatalytic Diels–Alder Trapping of Photochemically Generated Hydroxy-o-Quinodimethanes Dell Amico, Luca Vega-Penaloza, Alberto Cuadros, Sara Melchiorre, Paolo 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. 2019-02-27T15:29:15Z 2024-04-23T10:20:53Z 2019-02-27T15:29:15Z 2024-04-23T10:20:53Z 2019-02-27T15:29:15Z 2024-04-23T10:20:53Z 2016-01-19 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion http://hdl.handle.net/2072/350685 https://doi.org/10.1002/anie.201509472 eng info:eu-repo/grantAgreement/EC/FP7/278541 info:eu-repo/semantics/openAccess L'accés als continguts d'aquest document queda condicionat a l'acceptació de les condicions d'ús establertes per la següent llicència Creative Commons:http://creativecommons.org/licenses/by-nc-nd/4.0/ RECERCAT (Dipòsit de la Recerca de Catalunya)