1. A combined experimental and theoretical study of the thermal [3+2] cycloaddition of carbonyl ylides with activated alkenes
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Sandrine Ruchaud, Luis R. Domingo, Stéphane Fontanay, Raphaël E. Duval, Mar Ríos-Gutiérrez, Florence Mongin, Stéphane Bach, Thierry Roisnel, Stéphanie Philippot, Samira Hamza-Reguig, Ghenia Bentabed-Ababsa, Laboratoire de Synthèse Organique Appliquée, Universitat de València (UV), Structure et Réactivité des Systèmes Moléculaires Complexes (SRSMC), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Lorrain de Chimie Moléculaire (L2CM), Phophorylation de protéines et Pathologies Humaines (P3H), Station biologique de Roscoff [Roscoff] (SBR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Station biologique de Roscoff (SBR), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), CNRS, Centre National de la Recherche Scientifique, IUF, Institut Universitaire de France, 2016-78669, MINECO, Ministerio de Economía y Competitividad, Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Station biologique de Roscoff [Roscoff] (SBR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
- Subjects
Epoxide ,010402 general chemistry ,enones ,01 natural sciences ,Medicinal chemistry ,Analytical Chemistry ,Catalysis ,Inorganic Chemistry ,chemistry.chemical_compound ,[SDV.SP.MED]Life Sciences [q-bio]/Pharmaceutical sciences/Medication ,Cascade reaction ,[3+2] cycloaddition ,Enamines ,[CHIM]Chemical Sciences ,Tetrahydrofurans ,Spectroscopy ,theoretical calculations ,chemistry.chemical_classification ,[CHIM.ORGA]Chemical Sciences/Organic chemistry ,010405 organic chemistry ,Organic Chemistry ,Regioselectivity ,Cycloaddition ,0104 chemical sciences ,carbonyl ylides ,chemistry ,Ylide ,[SDV.MP.VIR]Life Sciences [q-bio]/Microbiology and Parasitology/Virology ,Stereoselectivity ,Cis–trans isomerism - Abstract
International audience; 4-Benzoyl-3,5-diaryltetrahydrofuran-2,2-dicarbonitriles were first synthesized from 2,2-dicyano-3-aryloxiranes and chalcones at toluene reflux; the 4,5-cis products proved to be predominantly formed and were isolated. Whereas shortened reaction times were observed by using microwave irradiation or catalytic cuprous chloride, no significant stereoselectivity change was in general noticed. Reacting 2,2-dicyano-3-aryloxiranes with 2-cyclopentenone next afforded 3-aryl-4-oxohexahydro-1H-cyclopenta[c]furan-1,1-dicarbonitriles, and the endo stereoisomers were isolated. That no stereoselectivity change was noticed in the presence of cuprous chloride rather suggests an impact of the salt on the epoxide ring opening. Finally, treatment of 2,2-dicyano-3-aryloxiranes by 2-morpholinoacrylonitrile yielded 3-cyano-3-morpholino-5-phenyltetrahydrofuran-2,2-dicarbonitriles from which the preponderant trans isomers were isolated. Importantly, the molecular mechanism of the domino reaction between 2,2-dicyano-3-phenyloxirane and 2-cyclopentenone was studied. The rate-determining thermal ring opening of the oxirane is followed by a non-concerted pseudoradical-type reaction of the carbonyl ylide with 2-cyclopentenone. Using the bond evolution theory also allowed the regioselectivity of this non-polar reaction to be explained.
- Published
- 2018
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