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

Harnessing visible light to access excited (triplet) states of organic compounds can enable impressive reactivity modes. This tutorial review covers the photophysical fundamentals and most significant advances in the field of visible-light-mediated energy transfer catalysis within the last decade. Methods to determine excited triplet state energies and to characterize the underlying Dexter energy transfer are discussed. Synthetic applications of this field, divided into four main categories (cyclization reactions, double bond isomerizations, bond dissociations and sensitization of metal complexes), are also examined.

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Energy transfer catalysis mediated by visible light: principles, applications, directions

In this Review article, we systematically summarize the design and applications of various kinds of long-lived emissive probes for bioimaging and biosensing via time-resolved photoluminescence techniques The probes reviewed, including lanthanides, transition-metal complexes, organic dyes, carbon and silicon nanoparticles, metal clusters, and persistent phosphores, exhibit longer luminescence lifetimes than that of autofluorescence from biological tissue and organs When these probes are internalized into living cells or animals, time-gated photoluminescence imaging selectively collects long-lived signals for intensity analysis, while photoluminescence lifetime imaging reports the decay details of each pixel Since the long-lived signals are differentiated from autofluorescence in the time domain, the imaging contrast and sensing sensitivity are remarkably improved The future prospects and challenges in this rapidly growing field are addressed

Long-Lived Emissive Probes for Time-Resolved Photoluminescence Bioimaging and Biosensing

For more than a decade the innovative field of homogeneous catalysis by gold was dominated by the interaction of the substrate molecule with one gold center, in most cases in mononuclear gold complexes. The initial interaction was typically a π-coordination of a carbon–carbon double bond to the gold, an activation of the unsaturated substrate molecule by a π-acidic metal center. Only recently clear evidence for reactions that involve the activation of organic substrates by two gold centers was obtained. In that new class of gold-catalyzed reactions the two gold centers interact with the substrate in a very different way. One gold complex is σ-bonded to a terminal alkynyl group in the substrate, the other one is π-coordinated. Only in a few cases, a combination π-coordination and σ-coordination to the same alkyne, which is the energetically preferred mode of interaction with two gold centers, initiates the reaction. In most of the cases, the reaction proceeds through an intermediate with one alkyne σ-bonde...

Dual gold catalysis.

N-Heterocyclic carbenes (NHCs) have become without doubt one of the most exciting and popular species in chemical science due to the ease of their preparation and modularity in stereoelectronic properties. Numerous types of NHCs have been prepared, and various experimental methodologies have been proposed for the study of their electronic properties in order to rationalize reactivities observed. The objective of this article is to provide a comprehensive overview of the most common and popular ones among them. In particular, these include the nickel(0)-based TEP, its rhodium(I) and iridium(I) variants, LEP and related electrochemical methods, the palladium(II)-based HEP, phosphinidene- and selenourea-based methods, as well as the use of direct 1J(C–H) coupling constants of the precarbene carbon in azolium salts. Each individual method and the underlying principle of detection it utilizes will be critically discussed in terms of strength and weakness. In addition, comprehensive amounts of data from various...

Electronic Properties of N-Heterocyclic Carbenes and Their Experimental Determination

Quantifying and understanding the steric properties of N-heterocyclic carbenes

selenoureas derived from a range of imidazol-2-ylidenes, 4,5-dihydroimidazol-2-ylidenes and triazol-2ylidenes are documented. Computational studies are used to explore the link between the shielding of the selenium centre and the electronic properties of the NHCs. Results show that dSe is correlated to the energy gap between a filled lone pair orbital on Se and the empty p* orbital corresponding to the Se–NHC bond. Bond energy decomposition analysis indicated no correlation between the orbital s-contribution to bonding and the chemical shielding, while a good correlation was found between the p-contribution to bonding and the chemical shielding, confirming that this technique is indeed able to quantify the ability of NHCs to accept p-electron density. Calculations conducted on phosphinidene adducts yielded similar results. With the link between dSe and dP and p-back bonding ability clearly established, these compounds represent useful ways in which to fully understand and quantify this aspect of the electronic properties of NHCs.

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What can NMR spectroscopy of selenoureas and phosphinidenes teach us about the π-accepting abilities of N-heterocyclic carbenes?

Straightforward synthesis of [Au(NHC)X] (NHC = N-heterocyclic carbene, X = Cl, Br, I) complexes.

Dinuclear Gold Catalysis: Are Two Gold Centers Better than One?

Sulfur-containing molecules participate in many essential biological processes. Of utmost importance is the methylthioether moiety, present in the proteinogenic amino acid methionine and installed in tRNA by radical-S-adenosylmethionine methylthiotransferases. Although the thiol-ene reaction for carbon-sulfur bond formation has found widespread applications in materials or medicinal science, a biocompatible chemo- and regioselective hydrothiolation of unactivated alkenes and alkynes remains elusive. Here, we describe the design of a general chemoselective anti-Markovnikov hydroalkyl/aryl thiolation of alkenes and alkynes-also allowing the biologically important hydromethylthiolation-by triplet-triplet energy transfer activation of disulfides. This fast disulfide-ene reaction shows extraordinary functional group tolerance and biocompatibility. Transient absorption spectroscopy was used to study the sensitization process in detail. The hereby gained mechanistic insights were successfully employed for optimization of the catalytic system. This photosensitized transformation should stimulate bioimaging applications and carbon-sulfur bond-forming late-stage functionalization chemistry, especially in the context of metabolic labelling.

Adrián Gómez-Suárez

Papers

Quantifying and understanding the steric properties of N-heterocyclic carbenes

What can NMR spectroscopy of selenoureas and phosphinidenes teach us about the π-accepting abilities of N-heterocyclic carbenes?

Straightforward synthesis of [Au(NHC)X] (NHC = N-heterocyclic carbene, X = Cl, Br, I) complexes.

Dinuclear Gold Catalysis: Are Two Gold Centers Better than One?

The energy-transfer-enabled biocompatible disulfide–ene reaction