Journal ArticleDOI
Copper(I)-catalyzed synthesis of azoles. DFT study predicts unprecedented reactivity and intermediates.
Fahmi Himo,Timothy Lovell,Robert Hilgraf,Vsevolod V. Rostovtsev,Louis Noodleman,K. Barry Sharpless,Valery V. Fokin +6 more
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TLDR
Huisgen's 1,3-dipolar cycloadditions become nonconcerted when copper(I) acetylides react with azides and nitrile oxides, providing ready access to 1,4-disubstituted 1,2, 3-triazoles and 3, 4-disubsided isoxazoles, respectively.Abstract:
Huisgen's 1,3-dipolar cycloadditions become nonconcerted when copper(I) acetylides react with azides and nitrile oxides, providing ready access to 1,4-disubstituted 1,2,3-triazoles and 3,4-disubstituted isoxazoles, respectively. The process is highly reliable and exhibits an unusually wide scope with respect to both components. Computational studies revealed a stepwise mechanism involving unprecedented metallacycle intermediates, which appear to be common for a variety of dipoles.read more
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Cu-catalyzed azide-alkyne cycloaddition.
TL;DR: The basis for the unique properties and rate enhancement for triazole formation under Cu(1) catalysis should be found in the high ∆G of the reaction in combination with the low character of polarity of the dipole of the noncatalyzed thermal reaction, which leads to a considerable activation barrier.
Journal ArticleDOI
Bioorthogonal Chemistry: Fishing for Selectivity in a Sea of Functionality
TL;DR: The bioorthogonal chemical reactions developed to date are described and how they can be used to study biomolecules.
Journal ArticleDOI
Organic Azides: An Exploding Diversity of a Unique Class of Compounds
TL;DR: In this Review, the fundamental characteristics of azide chemistry and current developments are presented and the focus will be placed on cycloadditions (Huisgen reaction), aza ylide chemistry, and the synthesis of heterocycles.
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Copper-catalyzed azide–alkyne cycloaddition (CuAAC) and beyond: new reactivity of copper(I) acetylides
Jason E. Hein,Valery V. Fokin +1 more
TL;DR: This tutorial review examines the history of the development of the CuAAC reaction, its key mechanistic aspects, and highlights the features that make it useful to practitioners in different fields of chemical science.
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‘Click’ Chemistry in Polymer and Materials Science
TL;DR: The metal catalyzed azide/alkyne "click" reaction (a variation of the Huisgen 1,3-dipolar cycloaddition reaction between terminal acetylenes and azides) represents an important contribution towards this endeavor.
References
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Density‐functional thermochemistry. III. The role of exact exchange
TL;DR: In this article, a semi-empirical exchange correlation functional with local spin density, gradient, and exact exchange terms was proposed. But this functional performed significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.
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Density-functional exchange-energy approximation with correct asymptotic behavior.
TL;DR: This work reports a gradient-corrected exchange-energy functional, containing only one parameter, that fits the exact Hartree-Fock exchange energies of a wide variety of atomic systems with remarkable accuracy, surpassing the performance of previous functionals containing two parameters or more.
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A New Mixing of Hartree-Fock and Local Density-Functional Theories
TL;DR: In this article, a new coupling of Hartree-Fock theory with local density functional theory was proposed to improve the predictive power of the Hartree−Fock model for molecular bonding, and the results of tests on atomization energies, ionization potentials, and proton affinities were reported.
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A stepwise huisgen cycloaddition process: copper(I)-catalyzed regioselective "ligation" of azides and terminal alkynes.
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Click Chemistry: Diverse Chemical Function from a Few Good Reactions.
TL;DR: In this paper, a set of powerful, highly reliable, and selective reactions for the rapid synthesis of useful new compounds and combinatorial libraries through heteroatom links (C-X-C), an approach called click chemistry is defined, enabled, and constrained by a handful of nearly perfect "springloaded" reactions.