Intermolecular Noncovalent Hydroxy-Directed Enantioselective Heck Desymmetrization of Cyclopentenol: Computationally Driven Synthesis of Highly Functionalized cis-4-Arylcyclopentenol Scaffolds

The Journal of Organic Chemistry
Juliana de Oliveira SilvaCarlos Roque D Correia

Abstract

New computationally driven protocols for the Heck desymmetrization of 3-cyclopenten-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-l 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.

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Citations

Jun 9, 2016·Chemistry : a European Journal·Francisco de AzambujaCarlos Roque D Correia
May 5, 2018·Chemistry : a European Journal·Juliana Manso de OliveiraCarlos Roque Duarte Correia
Oct 6, 2018·Chemistry : a European Journal·Shivashankar KattelaCarlos Roque D Correia
Dec 1, 2018·ChemistryOpen·Efimov IlyaLeonid Voskressensky
Jun 27, 2021·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Caio C Oliveira, Carlos Roque Duarte Correia
Dec 19, 2018·Journal of the American Chemical Society·Yernaidu ReddiRaghavan B Sunoj
Jan 31, 2020·Organic Letters·Peizhong XieTeck-Peng Loh
Oct 5, 2021·Bioorganic & Medicinal Chemistry Letters·Jailton de Souza-FerrariDemetrius Antonio Machado de Araújo

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