1.1. General Reactivity of Alkyne-Gold(I) Complexes
For centuries, gold had been considered a precious, purely decorative inert metal. It was not until 1986 that Ito and Hayashi described the first application of gold(I) in homogeneous catalysis.1 More than one decade later, the first examples of gold(I) activation of alkynes were reported by Teles2 and Tanaka,3 revealing the potential of gold(I) in organic synthesis. Now, gold(I) complexes are the most effective catalysts for the electrophilic activation of alkynes under homogeneous conditions, and a broad range of versatile synthetic tools have been developed for the construction of carbon–carbon or carbon–heteroatom bonds.

Gold(I) complexes selectively activate π-bonds of alkynes in complex molecular settings,4−10 which has been attributed to relativistic effects.11−13 In general, no other electrophilic late transition metal shows the breadth of synthetic applications of homogeneous gold(I) catalysts, although in occasions less Lewis acidic Pt(II) or Ag(I) complexes can be used as an alternative,9,10,14,15 particularly in the context of the activation of alkenes.16,17 Highly electrophilic Ga(III)18−22 and In(III)23,24 salts can also be used as catalysts, although often higher catalyst loadings are required.

In general, the nucleophilic Markovnikov attack to η2-[AuL]+-activated alkynes 1 forms trans-alkenyl-gold complexes 2 as intermediates (Scheme 1).4,5a,9,10,12,25−29 This activation mode also occurs in gold-catalyzed cycloisomerizations of 1,n-enynes and in hydroarylation reactions, in which the alkene or the arene act as the nucleophile.



Scheme 1

Anti-Nucleophilic Attack to η2-[AuL]+-Activated Alkynes

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Gold(I)-Catalyzed Activation of Alkynes for the Construction of Molecular Complexity

This article aims to show the identity of “circularly polarized luminescent active simple organic molecules” as a new concept in organic chemistry due to the potential interest of these molecules, as availed by the exponentially growing number of research articles related to them. In particular, it describes and highlights the interest and difficulty in developing chiral simple (small and non-aggregated) organic molecules able to emit left- or right-circularly polarized light efficiently, the efforts realized up to now to reach this challenging objective, and the most significant milestones achieved to date. General guidelines for the preparation of these interesting molecules are also presented.

/pdf/circularly-polarized-luminescence-from-simple-organic-5gfpxas9he.pdf

Circularly Polarized Luminescence from Simple Organic Molecules

Circularly Polarized Luminescence and Circular Dichroisms in Small Organic Molecules: Correlation between Excitation and Emission Dissymmetry Factors

Recent Progress on Circularly Polarized Luminescent Materials for Organic Optoelectronic Devices

This review is focused on the analysis of current data on new methods of alkenylation of arenes and heteroarenes with alkynes by transition metal catalyzed reactions, Bronsted/Lewis acid promoted transformations, and others. The synthetic potential, scope, limitations, and mechanistic problems of the alkenylation reactions are discussed. The insertion of an alkenyl group into aromatic and heteroaromatic rings by inter- or intramolecular ways provides a synthetic route to derivatives of styrene, stilbene, chalcone, cinnamic acid, various fused carbo- and heterocycles, etc.

Alkenylation of Arenes and Heteroarenes with Alkynes.

Facile Synthetic Route to Highly Luminescent Sila[7]helicene

Synthesis and Properties of [7]Helicene-like Compounds Fused with a Fluorene Unit.

A new method for producing a dispersed gold nanoparticle (Au NP) array to anchor probe DNAs onto a DNA-sensing electrode has been developed. A homogenous gold sulfide (Au2S) core (precursor of Au NP) was biomineralized in the cavity of a mutant apoferritin (K98E) with enhanced negative outer-surface charges. We employed a slow chemical reaction system utilizing a stable cationic gold complex. K98E could attract the gold complex, and Au2S NPs were synthesized. K98E enabled dispersed placement of the synthesized Au2S core onto a cationic 3-aminopropyltriethoxysilane (APTES) layer on a substrate. UV–ozone treatment eliminated the protein shells and APTES layer. X-ray photoelectron spectroscopy confirmed that the Au2S core was reduced to Au NPs under the same treatment. Atomic force microscopy (AFM) clearly showed that the combination of apoferritin versatility, chemical system design, and UV–ozone treatment successfully produced a dispersed Au NP array on the substrate.

Dispersed Gold Nanoparticle Array Produced by Apoferritins Utilizing Biomineralization and Chemical Conversion

PCR under Low Ionic Concentration Buffer Conditions

The resistance of silane-based monolayers was investigated under polymerase chain reaction (PCR) thermal conditions. The monolayers of (3-glycidyloxypropyl)trimethoxysilane (GPTMS) were fabricated ...

Kazuyuki Nobusawa

Papers

Facile Synthetic Route to Highly Luminescent Sila[7]helicene

Synthesis and Properties of [7]Helicene-like Compounds Fused with a Fluorene Unit.

Dispersed Gold Nanoparticle Array Produced by Apoferritins Utilizing Biomineralization and Chemical Conversion

PCR under Low Ionic Concentration Buffer Conditions

Hydrolytically Stable Monolayers Derived from Epoxy Silane