Computational Insight into 1,2-Diamine, -Diether, and -Amino Ether Chiral Ligand-Mediated Carbolithiation: A Case of Enantioinduction Reversal
| Autor: | Anne Boussonnière, Anne-Sophie Castanet, Hélène Guyon |
|---|---|
| Přispěvatelé: | Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) |
| Rok vydání: | 2020 |
| Předmět: |
[CHIM.ORGA]Chemical Sciences/Organic chemistry
010405 organic chemistry Ligand Stereochemistry Organic Chemistry Chiral ligand Diastereomer Ether 010402 general chemistry 01 natural sciences Asymmetric induction 0104 chemical sciences chemistry.chemical_compound chemistry Intramolecular force Diamine Stereoselectivity ComputingMilieux_MISCELLANEOUS |
| Zdroj: | Journal of Organic Chemistry Journal of Organic Chemistry, American Chemical Society, 2020, 85 (14), pp.8933-8943. ⟨10.1021/acs.joc.0c00832⟩ |
| ISSN: | 1520-6904 0022-3263 |
| Popis: | trans-1,2-Cyclohexanediamine, -diether, and -amino ether were compared as chiral inducers in the asymmetric intramolecular carbolithiation of olefinic aryllithiums. Switching from diamine to ethereal ligands inverts the sense of asymmetric induction. This reversal of stereoselectivity was investigated through density functional theory calculations. High enantioselectivities observed with diether and amino ether ligands arise from favorable weak interactions between the ligand and the substrate. The relative efficiency of the three ligands and sense of stereoinduction for the most efficient diether and amino ether ligands prove to be foreseeable by modeling the reaction with the parent achiral 1,2-bidentate additives and comparing the diastereomeric transition states stemming from the two half-chair conformations of their lithium chelate. |
| Databáze: | OpenAIRE |
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