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Type: Artigo
Title: Intermolecular Noncovalent Hydroxy-directed Enantioselective Heck Desymmetrization Of Cyclopentenol: Computationally Driven Synthesis Of Highly Functionalized Cis-4-arylcyclopentenol Scaffolds
Author: Silva
Juliana de Oliveira; Angnes
Ricardo A.; Menezes da Silva
Vitor H.; Servilha
Bruno M.; Adeel
Muhammad; Braga
Ataualpa A. C.; Aponick
Aaron; Correia
Carlos Roque D.
Abstract: New computationally driven protocols for the Heck desymmetrization of 3-cydopenten-1-ol with aryldiazonium tetrafluoroborates were developed. These new conditions furnished remarkable product selectivity originating from a resident hydroxyl group and the critical choice of the reaction solvent. Mechanistic insights gleaned from theoretical calculations of the putative transition states predicted toluene as an adequate solvent choice to attain high enantioselectivity by strengthening the noncovalent interaction of the substrate hydroxyl group and the chiral cationic palladium catalyst. Laboratory experiments validated the theoretical predictions, and by employing 2% MeOH/toluene as solvent, the Heck-Matsuda reaction provided exclusively the cis-4-arylcyclopentenols 3a-1 in good to excellent yields in enantiomeric excesses up to 99%. The performance of the new PyOx ligand (S)-4-tert-butyl-2-(3,5-dichloropyridin-2-yl)-4,5-dihydrooxazole was also successfully evaluated in the Heck-Matsuda desymmetrization of 3-cyclopenten-1-ol. The synthetic potential of these highly functionalized cis-4-arylcyclopentenols is illustrated by a gold-catalyzed synthesis of cyclopenta[b]benzofuran skeletons.
Editor: Amer Chemical Soc
Rights: fechado
Identifier DOI: 10.1021/acs.joc5b02846
Date Issue: 2016
Appears in Collections:Unicamp - Artigos e Outros Documentos

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