scholarly journals Copper-catalyzed carbo-difluoromethylation of alkenes via radical relay

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Aijie Cai ◽  
Wenhao Yan ◽  
Xiaojun Zeng ◽  
Samson B. Zacate ◽  
Tzu-Hsuan Chao ◽  
...  
Keyword(s):  
Late Stage ◽  
Density Functional ◽  
Organic Molecules ◽  
Functional Group ◽  
Density Functional Theory Calculations ◽  
Bioactive Molecules ◽  
Mechanistic Studies ◽  
Ligand Effect ◽  
Functional Theory ◽  
Complex Molecules

AbstractOrganic molecules that contain alkyl-difluoromethyl moieties have received increased attention in medicinal chemistry, but their synthesis in a modular and late-stage fashion remains challenging. We report herein an efficient copper-catalyzed radical relay approach for the carbo-difluoromethylation of alkenes. This approach simultaneously introduces CF2H groups along with complex alkyl or aryl groups into alkenes with regioselectivity opposite to traditional CF2H radical addition. We demonstrate a broad substrate scope and a wide functional group compatibility. This scalable protocol is applied to the late-stage functionalization of complex molecules and the synthesis of CF2H analogues of bioactive molecules. Mechanistic studies and density functional theory calculations suggest a unique ligand effect on the reactivity of the Cu-CF2H species.

scholarly journals CO2 activation and dissociation on the low miller index surfaces of pure and Ni-coated iron metal: a DFT study

2017 ◽  
Vol 19 (29) ◽  
pp. 19478-19486 ◽  
Author(s):  
Caroline R. Kwawu ◽  
Richard Tia ◽  
Evans Adei ◽  
Nelson Y. Dzade ◽  
C. Richard A. Catlow ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Dft Study ◽  
Co2 Activation ◽  
Mechanistic Studies ◽  
Functional Theory ◽  
Miller Index ◽  
Iron Metal ◽  
Spin Polarized

We have used spin polarized density functional theory calculations to perform extensive mechanistic studies of CO2 dissociation into CO and O on the clean Fe(100), (110) and (111) surfaces and on the same surfaces coated by a monolayer of nickel.

scholarly journals Water adsorption on bimetallic PtRu/Pt(111) surface alloys

2016 ◽  
Vol 472 (2194) ◽  
pp. 20160618 ◽  
Author(s):  
Julia M. Fischer ◽  
David Mahlberg ◽  
Tanglaw Roman ◽  
Axel Groß
Keyword(s):  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Alloy Layer ◽  
Surface Alloy ◽  
Water Molecules ◽  
Surface Alloys ◽  
Ligand Effect ◽  
Functional Theory ◽  
Adsorption Of Water ◽  
Dynamics Simulations

The adsorption of water on bimetallic PtRu/Pt(111) surface alloys has been studied based on periodic density functional theory calculations including dispersion corrections. The Ru atoms of the PtRu surface alloy interact more strongly with water than Pt atoms, as far as both single water molecules and ice-like hexagonal structures are concerned. Within the surface alloy layer, the lateral ligand effect reducing the local reactivity of the surface atoms with increasing Ru content is more dominant than the opposing geometric effect due to the tensile strain. The structural preference for the Ru atoms also prevails at room temperature, as ab initio molecular dynamics simulations show.

scholarly journals Solvent-controlled photocatalytic divergent cyclization of alkynyl aldehydes: access to cyclopentenones and dihydropyranols

2021 ◽  
Author(s):  
Haiqian Zhu ◽  
Hanliang Zheng ◽  
Junhua Zhang ◽  
Jian Feng ◽  
Lichun Kong ◽  
...  
Keyword(s):  
Density Functional ◽  
Hydrogen Transfer ◽  
Density Functional Theory Calculations ◽  
Bioactive Molecules ◽  
Molecular Scaffolds ◽  
Reaction Conditions ◽  
Direct Construction ◽  
Functional Theory ◽  
Alkoxy Radicals ◽  
Powerful Strategy

Abstract Divergent synthesis is a powerful strategy for the fast assembly of different molecular scaffolds from the identical starting materials. We describe here a novel solvent-controlled photocatalytic divergent cyclization of alkynyl aldehydes with sulfonyl chlorides for the direct construction of highly functionalized cyclopentenones and dihydropyranols that widely exist in bioactive molecules and natural products. Density functional theory calculations suggest that an unprecedented N,N-dimethylacetamide-assisted 1,2-hydrogen transfer of alkoxy radicals is responsible for the cyclopentenone formation, whereas a C-C cleavage accounts for the selective production of dihydropyranols in acetonitrile. Given the simple and mild reaction conditions, excellent functional group compatibility, forming up to four chemical bonds, and tunable selectivity, it may find wide applications in synthetic chemistry.

Adsorption of alcohols and hydrocarbons on nonstoichiometric cementite{010} surfaces

2018 ◽  
Vol 20 (20) ◽  
pp. 14133-14144 ◽  
Author(s):  
David Muñoz Ramo ◽  
Stephen J. Jenkins
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Organic Molecules ◽  
Van Der Waals ◽  
Density Functional Theory Calculations ◽  
Functional Theory

We investigate the adsorption of several organic molecules on a nonstoichiometric {010} surface of Fe3C (cementite) by means of density functional theory calculations with van der Waals corrections.

scholarly journals Mechanistic Studies of Cyclopentadienyl Ring-Slippage: A TRIR and DFT Study via Photolysis of (η1-C5Cl5)Mn(CO)5

2018 ◽  
Author(s):  
Justin Lomont ◽  
Son Nguyen ◽  
Charles Harris
Keyword(s):  
Density Functional ◽  
Solvent Molecule ◽  
Density Functional Theory Calculations ◽  
Organometallic Complexes ◽  
Mechanistic Studies ◽  
Functional Theory ◽  
Organometallic Reactions ◽  
Ligand Dissociation ◽  
Nonpolar Solvents ◽  
Uv Excitation

<div>Ring slip is among the most widely invoked ligand distortions in organometallic chemistry, yet very few ring slipped geometries have been directly characterized. Here we investigate the ultrafast photochemistry of (η1-C5Cl5)Mn(CO)5 to characterize the “reverse ring-slip” processes that result upon ligand dissociation from this complex in polar and nonpolar solvents. (η1- C5Cl5)Mn(CO)5 readily undergoes dicarbonyl-loss upon photoexcitation across a range of UV-excitation wavelengths, and the fac- ile ejection of a second-CO during the reverse ring-slip process is shown to occur due to a mechanism that relies on the enthalpy released during the reverse ring-slip. This mechanistic paradigm is potentially widespread in organometallic reactions involving changes in ligand hapticity, carrying implications for the expansive range of Cp-ligated organometallic complexes. Experiments in CH2Cl2 solution observe formation of a solvent-coordinated product upon coordination of CH2Cl2 to the monocarbonyl-loss spe- cies. An energetic barrier to solvent coordination is present due to the need for rearrangement of the ring geometry from a three- center M-C-Cl coordination to η1 coordination to accommodate the incoming solvent molecule. Density functional theory calculations are used to investigate the structures of the experimentally observed intermediates, as well as to explore the relevance of these experiments to analogous complexes containing the more commonly encountered Cp (C5H5) and Cp* (C5Me5) cyclopentadienyl ligands. </div><div><br></div>

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