DFT study of Ni/NHC-catalyzed C–H alkylation of fluoroarenes with alkenes to synthesize fluorotetralins: mechanism, chemoselectivity of C–H vs. C–F bond activation, and regio- and enantioselectivities of C–H bond activation
- 1 February 2021
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Organic Chemistry Frontiers
- Vol. 8 (7), 1520-1530
- https://doi.org/10.1039/d0qo01594f
Abstract
Density functional theory calculations have been carried out to elucidate the mechanism, enantio-, regio-, and chemoselectivities, and the role of the NHC ligand in the Ni/NHC-catalyzed alkylation of fluoroarenes with alkenes, a new strategy that exclusively achieved enantio- and regioselective C–H activation over multiple C–F bonds (Angew. Chem., Int. Ed., 2019, 58, 13433–13437). The reaction is found to follow a concerted ligand–ligand hydrogen transfer (LLHT) mechanism instead of the stepwise oxidative addition/alkene insertion mechanism. The high R-enantioselectivity originates from the stronger agostic interaction in the R-configuration than that in the S-type enantiomer, the exclusive endo-regioselectivity is controlled by the stronger electrostatic force of the Ni(0) catalyst with the terminal carbon atom than that with the internal carbon atom in the alkene, and the excellent chemoselectivity of C–H activation over C–F activation is attributed to the more favorable concerted ligand–ligand hydrogen transfer (LLHT) mechanism of C–H activation than the stepwise mechanism of the C–F activation. The enhanced reactivity with the NHC ligand is attributed to the increase in the HOMO level of the catalyst via the highly electron-donating effect of the NHC ligand.Keywords
Funding Information
- National Natural Science Foundation of China (21773139, 21833004)
This publication has 51 references indexed in Scilit:
- Metal‐Free Cross‐Dehydrogenative Coupling of Heterocycles with AldehydesAngewandte Chemie-International Edition, 2013
- C−F and C−H Bond Activation of Fluorobenzenes and Fluoropyridines at Transition Metal Centers: How Fluorine Tips the ScalesAccounts of Chemical Research, 2011
- A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-PuThe Journal of Chemical Physics, 2010
- C—H Bond Activation in Transition Metal Species from a Computational PerspectiveChemical Reviews, 2010
- Distortion/Interaction Energy Control of 1,3-Dipolar Cycloaddition ReactivityJournal of the American Chemical Society, 2007
- Design, Synthesis and Physical Properties of New Liquid Crystal Materials Having a Fluoro-Substituted Tetrahydronaphthalene Structure for Active Matrix LCDMolecular Crystals and Liquid Crystals, 2004
- Catecholamine modulatory effects of nepicastat (RS‐25560‐197), a novel, potent and selective inhibitor of dopamine‐β‐hydroxylaseBritish Journal of Pharmacology, 1997
- Novel (R)-2-Amino-5-fluorotetralins: Dopaminergic Antagonists and Inverse AgonistsJournal of Medicinal Chemistry, 1996
- Energy-adjustedab initio pseudopotentials for the second and third row transition elementsTheoretical Chemistry Accounts, 1990
- Formulation of the reaction coordinateThe Journal of Physical Chemistry, 1970