Journal ArticleDOI
Mechanisms of the Au- and Pt-catalyzed intramolecular acetylenic Schmidt reactions: a DFT study.
TLDR
The reaction mechanisms of the PtCl 4- and Au(I)-catalyzed intramolecular acetylenic Schmidt reactions were analyzed by means of hybrid density functional calculations at the B3LYP/6-31G*(LANL2DZ) level of theory for better understanding of the acceleration effect of ethanol solvent in PtCl4- catalyzed reaction and the different catalytic activities of Au and Pt catalysts.Abstract:
The reaction mechanisms of the PtCl4- and Au(I)-catalyzed intramolecular acetylenic Schmidt reactions were analyzed by means of hybrid density functional calculations at the B3LYP/6-31G*(LANL2DZ) level of theory for better understanding of the acceleration effect of ethanol solvent in PtCl4-catalyzed reaction and the different catalytic activities of Au and Pt catalysts. Calculations indicate the rate of the PtCl4-catalyzed reaction in noncoordinative solvent of 1,2-dichloroethane is limited by isomerization of the relatively stable chelate complex to the reactive π-complex of PtCl4 with the acetylenic moiety of homopropargyl azide substrate, which requires an activation energy of 29.6 kcal/mol. All nucleophilic cyclization, dinitrogen elimination, and 1,2-H shift of metal-carbene steps are quite facile. The generation of 2H-pyrrole intermediate in PtCl4-catalyzed reaction is completed by a ligand substitution reaction, and the final 2H-pyrrole to 1H-pyrrole isomerization is an intermolecular process with...read more
Citations
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Transition Metal-Mediated Synthesis of Monocyclic Aromatic Heterocycles
TL;DR: The present review is a transition metal-catalyzed synthesis of aromatic monocyclic heterocycles, aiming at achieving greater levels of molecular complexity and better functional group compatibilities in a convergent and atom economical fashions from readily accessible starting materials and under mild reaction conditions.
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Late transition metal-catalyzed hydroamination and hydroamidation.
Journal ArticleDOI
Gold‐Catalyzed Transformation of 2‐Alkynyl Arylazides: Efficient Access to the Valuable Pseudoindoxyl and Indolyl Frameworks
Alexander Wetzel,Fabien Gagosz +1 more
TL;DR: A series of functionalized 2-alkynyl arylazides has been converted into 3-substituted indoles or 2,2-disubstituting indolin-3-ones in the presence of a gold(I) complex to trap the intermediate a-imino gold carbene.
Journal ArticleDOI
Assessment of Theoretical Methods for Complexes of Gold(I) and Gold(III) with Unsaturated Aliphatic Hydrocarbon: Which Density Functional Should We Choose?
TL;DR: This study uses high-level coupled cluster calculations with core-valence correlation and complete basis set (CBS) limit extrapolation as a reference, for assessing the performance of popular density functional theory approximations for a variety of Au(I)/Au(III) complexes with unsaturated aliphatic hydrocarbon CnHm substrates.
Journal ArticleDOI
Nucleophilic Nitrenoids Through π‐Acid Catalysis: Providing a Common Basis for Rapid Access into Diverse Nitrogen Heterocycles
Paul W. Davies,Miguel Garzón +1 more
TL;DR: In this paper, different nucleophilic nitrenoid types are explored showing how they can be used across a range of (poly)cyclization and formal cycloaddition processes to provide an alternative and direct disconnection pathway in the generation of N-heterocyclic motifs.
References
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Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
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Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals
P. Jeffrey Hay,Willard R. Wadt +1 more
TL;DR: In this article, effective core potentials (ECP) have been derived to replace the innermost core electron for third row (K), fourth row (Rb-Ag), and fifth row (Cs-Au) atoms.
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Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
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