DFT Mechanistic Insights into the Ni(II)-Catalyzed Enantioselective Arylative Cyclization of Tethered Allene-Ketones.

Autor: Chao CBE; School of Chemistry and Molecular Bioscience, University of Wollongong, Wollongong, NSW 2522, Australia.; Molecular Horizons, University of Wollongong, Wollongong, NSW 2522, Australia., Pyne SG; School of Chemistry and Molecular Bioscience, University of Wollongong, Wollongong, NSW 2522, Australia.; Molecular Horizons, University of Wollongong, Wollongong, NSW 2522, Australia., Hyland CJT; School of Chemistry and Molecular Bioscience, University of Wollongong, Wollongong, NSW 2522, Australia.; Molecular Horizons, University of Wollongong, Wollongong, NSW 2522, Australia., Lee R; School of Chemistry and Molecular Bioscience, University of Wollongong, Wollongong, NSW 2522, Australia.; Molecular Horizons, University of Wollongong, Wollongong, NSW 2522, Australia.
Jazyk: angličtina
Zdroj: Chemistry, an Asian journal [Chem Asian J] 2023 Nov 02; Vol. 18 (21), pp. e202300724. Date of Electronic Publication: 2023 Sep 25.
DOI: 10.1002/asia.202300724
Abstrakt: Density functional theory (DFT) has provided a detailed mechanistic picture for the redox neutral nickel(II)-catalyzed arylative cyclization reactions of a tethered allene-ketone with arylboronic acids. A mechanistic rationale for the high diastereo- and enantioselectivity achieved experimentally at high reaction temperature was uncovered through modeling the reaction with a chiral ligand and the predicted stereochemical outcome corroborates with experimental results. An unprecedented mechanism for the base-free organoboron transmetalation was revealed and the regioselectivity of migratory insertion of tethered allene-ketones as well as the stability of the possible allylnickel isomers (σ-allyl vs π-allyl) were clarified. The multifaceted nature of the reaction is revealed with certain elementary steps preferring cationic compared to the neutral state.
(© 2023 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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