Expanding Stereoelectronic Limits of <i>endo</i>-<i>tet</i> Cyclizations: Synthesis of Benz[<i>b</i>]azepines from Donor–Acceptor Cyclopropanes
Anna E. Vartanova, Andrey Yu. Plodukhin, Nina K Ratmanova, Ivan A Andreev, Mikhail N. Anisimov, Nikita B. Gudimchuk, Victor B. Rybakov, Ирина И. Левина, Оlga А. Ivanova, Igor V. Trushkov, Igor V. Alabugin
Abstract
]azepin-2-ones in high yields. The reaction proceeds with the inversion of the configuration at the electrophilic carbon. In this process, a formally six-membered transition state yields a seven-membered ring as the pre-existing cycle is merged into the forming ring. The stereochemistry of the products can be controlled by the reaction time and by the nature of Lewis acid, opening access to both diastereomers by tuning of the reaction conditions.
Topics & Concepts
ChemistryIntramolecular forceElectrophileLewis acids and basesStereochemistryNucleophileMoietyRing (chemistry)AcceptorDiastereomerMedicinal chemistryCatalysisOrganic chemistryCondensed matter physicsPhysicsCyclopropane Reaction MechanismsCatalytic Alkyne ReactionsAsymmetric Synthesis and Catalysis