Acetylenic Coupling: A Powerful Tool in Molecular Construction

Siemsen, Peter; Livingston, R. C.; Diederich, François

doi:10.1002/1521-3773(20000804)39:15<2632::aid-anie2632>3.3.co;2-6

Cited by 463 publications

(659 citation statements)

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“…Quite surprisingly, despite the wide and diverse use of acetylene ''building blocks'' in solution-phase chemistry, 165 there are few published studies, apart from CuAAC reactions, that have reported on the unique properties of the carbon-carbon triple bond in the context of derivatizing solid substrates. We predict alkyne-alkyne coupling will become increasingly popular.…”

Section: Acetylenic Couplingmentioning

confidence: 99%

The molecular level modification of surfaces: from self-assembled monolayers to complex molecular assemblies

2011

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The modification of surfaces with self-assembled monolayers (SAMs) containing multiple different molecules, or containing molecules with multiple different functional components, or both, has become increasingly popular over the last two decades. This explosion of interest is primarily related to the ability to control the modification of interfaces with something approaching molecular level control and to the ability to characterise the molecular constructs by which the surface is modified. Over this time the level of sophistication of molecular constructs, and the level of knowledge related to how to fabricate molecular constructs on surfaces have advanced enormously. This critical review aims to guide researchers interested in modifying surfaces with a high degree of control to the use of organic layers. Highlighted are some of the issues to consider when working with SAMs, as well as some of the lessons learnt (169 references). 2011 The Royal Society of Chemistry. The modification of surfaces with self-assembled monolayers (SAMs) containing multiple different molecules, or containing molecules with multiple different functional components, or both, has become increasingly popular over the last two decades. This explosion of interest is primarily related to the ability to control the modification of interfaces with something approaching molecular level control and to the ability to characterise the molecular constructs by which the surface is modified. Over this time the level of sophistication of molecular constructs, and the level of knowledge related to how to fabricate molecular constructs on surfaces have advanced enormously. This critical review aims to guide researchers interested in modifying surfaces with a high degree of control to the use of organic layers. Highlighted are some of the issues to consider when working with SAMs, as well as some of the lessons learnt (169 references).

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Section: Acetylenic Couplingmentioning

confidence: 99%

The molecular level modification of surfaces: from self-assembled monolayers to complex molecular assemblies

2011

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“…[237] First attempts using a classical Sonogashira cross coupling protocol mainly provided diacetylenes as product, probably due to a copper ion catalyzed oxidative acetylene homo-coupling reaction. [245] [246] To avoid this competing homo-coupling protocol was chosen. [147] It has to be mentioned that copper ions were added.…”

Section: General Protocol For the Sonogashira Cross Coupling Reactionmentioning

confidence: 99%

Shape‐Switchable Azo‐Macrocycles

et al. 2009

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The synthesis of four shape‐switchable macrocycles comprising different peripheral substituents is described. The macrocycles 1–4 consist of m‐terphenyl semicircles interlinked by two azo joints. These macrocycles were assembled from nitro‐functionalized m‐terphenyl moieties through reductive dimerization. The semicircles were assembled through Suzuki cross‐coupling reactions. The molecular weights of the macrocycles were determined by vapour pressure osmometry, because mass spectrometry failed in the cases of 2 and 3. The E → Z photoisomerization reactions were analysed by UV/Vis spectroscopy complemented by 1H NMR studies. A very slow thermal back‐reaction indicated considerable stabilization of the Z isomer. The reduced efficiency of the thermal back‐reaction probably arises from the reduced degree of freedom due to the mechanical interlinking of the two azo groups. The photostationary state consisted of all‐Z (85 %) and all‐E isomers (15 %). The E → Z transformation induced by irradiation displayed simple exponential kinetics, which indicates pairwise switching of the two azo groups in a macrocycle, at least on the timescale under investigation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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“…[6] We hypothesized that the catalytic copper(I) species is generated upon reduction of copper(II) by either an oxidizable solvent such as methanol [7] or the terminal alkyne substrate by means of the oxidative homocoupling reaction. [8] A subset of the azide substrates rapidly convert to triazole products under the CuA C H T U N G T R E N N U N G (OAc) 2 -mediated conditions. Those azides, which are termed "chelating azides," contain auxiliary ligands capable of assisting the azido group in binding the copper centre.…”

Section: Introductionmentioning

confidence: 99%

Ligand‐Assisted, Copper(II) Acetate‐Accelerated Azide–Alkyne Cycloaddition

Michaels

Zhu

2011

Chemistry An Asian Journal

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Polytriazole ligands such as the widely used tris[(1‐benzyl‐1 H‐1,2,3‐triazol‐4‐yl)methyl]amine (TBTA), are shown to assist copper(II) acetate‐mediated azide–alkyne cycloaddition (AAC) reactions that involve nonchelating azides. Tris(2‐{4‐[(dimethylamino)methyl]‐1 H‐1,2,3‐traizol‐1‐yl}ethyl)amine (DTEA) outperforms TBTA in a number of reactions. The satisfactory solubility of DTEA in a wide range of polar and nonpolar solvents, including water and toluene, renders it advantageous under copper(II) acetate‐mediated conditions. The copper(II) acetate‐mediated formation of the three triazolyl groups in a tris(triazolyl)‐based ligand occurs sequentially with an inhibitory effect in the last step. The kinetic investigations of the ligand‐assisted reactions reveal an interesting mechanistic dependence on the relative affinity of azide and alkyne to copper (II). In addition to expanding the scope of the copper(II) acetate‐mediated AAC reactions to include nonchelating azides, this work offers evidence for the mechanistic synergy between the title reaction and the alkyne oxidative homocoupling reaction. The elucidation of the structural details of the polytriazole‐ligand‐bound reactive species in copper(I/II)‐mediated AAC reactions, however, awaits further characterization of the metal coordination chemistry of polytriazole ligands.

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Acetylenic Coupling: A Powerful Tool in Molecular Construction

Cited by 463 publications

References 0 publications

The molecular level modification of surfaces: from self-assembled monolayers to complex molecular assemblies

The molecular level modification of surfaces: from self-assembled monolayers to complex molecular assemblies

Shape‐Switchable Azo‐Macrocycles

Ligand‐Assisted, Copper(II) Acetate‐Accelerated Azide–Alkyne Cycloaddition

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