Conformational diversity of 1‑chloro-1-chloromethylsilacyclohexane with experimental (Raman and IR) and computational (DFT, MP2) methods

Stocka, J.; Platakyté, Rasa; McFadden, Thomas M. C.; Čeponkus, Justinas; Aleksa, Valdemaras; Hanna, Atef G.; Šablinskas, Valdas; Rodziewicz, Paweł; Guirgis, Gamil A.

doi:10.1016/j.molstruc.2021.131644

Cited by 3 publications

(1 citation statement)

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“…In the remaining structures, only four carbon atoms of the six-membered ring form one plane, and the carbon atoms C3A (C4A) and C9A (C7A) deviate from it by −(0.330–0.392) and 0.287–0.346 Å, respectively (for atom numeration, see the SI). Thus, it shows that the central cyclohexene ring in all heterocycles adopts a half-chair conformation . Therefore, all hydrogen atoms in the cyclohexene ring are positioned pseudoaxially (perpendicular to the plane of the parent ring), except for the hydrogen atom in the α-position to the carboxyl group (this pseudoequatorial hydrogen atom is aligned nearly parallel to the plane of the ring).…”

Section: Resultsmentioning

confidence: 99%

Domino Three-Component N-Acylation/[4 + 2] Cycloaddition/Alder-ene Synthesis of Polysubstituted Benzo[f]isoindole-4-carboxylic Acids

Alekseeva,

Nadirova,

Zaytsev

et al. 2023

J. Org. Chem.

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Diversely substituted, partially saturated benzo[f ]isoindole-4-carboxylic acids were synthesized by a new threecomponent reaction (3CR) starting from cinnamic amines (3-arylallylamines), maleimides, and maleic anhydride. The process consists of N-acylation of the amines by maleic anhydride, intramolecular [4 + 2] cycloaddition in vinylarenes (the IMDAV reaction), and the concluding Alder-ene reaction between Diels−Alder intermediates and maleimides. All of the reaction steps proceed in a highly regio-and stereoselective manner, furnishing five adjacent chiral centers and leading to a single diastereoisomer of the title compound. The efficiency of the transformation is secured by thermal conditions or utilization of soft Lewis acids (Yb(OTf) 3 ) as catalysts. The kinetics and mechanism of the 3CR were studied by using dynamic 19 F NMR. Based on the NMR data and density functional theory (DFT) calculations, the IMDAV, not the Alder-ene, reaction is the rate-limiting step of the entire process.

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Section: Resultsmentioning

confidence: 99%