In this critical review the reactivity patterns observed with different types of diyne substrates in gold catalysis are discussed. Apart from the many examples from homogeneous catalysis, the few examples from heterogeneous gold catalysis are also included. With a proper arrangement of the two alkynes unique and exciting reactivity patterns like 1,3-carbonyl transpositions, carbene transfer reactions, cascade annulations, macrocyclisations or the formation of gold vinylidene intermediates are observed. These reactions are of interest for organic synthesis, for pharmaceutical and medicinal chemistry and for material science.

Gold-catalysed reactions of diynes

An efficient yttrium-catalyzed intramolecular hydroalkoxylation/Claisen rearrangement sequence has been achieved, thus enabling facile access to a diverse array of valuable medium-sized lactams. Furthermore, a mechanistic rationale for this novel cascade reaction is well supported by a variety of control experiments.

Yttrium‐Catalyzed Intramolecular Hydroalkoxylation/Claisen Rearrangement Sequence: Efficient Synthesis of Medium‐Sized Lactams

Synthesis of Spiroaminals and Spiroketals with Bimetallic Relay Catalysis

A series of arylynamides with alkyloxy groups at the ortho position of the aryl group was prepared through a short alkylation/cross-coupling/amidation sequence. The gold-catalyzed conversion of these substrates combined both CO and CC formation steps, thus providing benzofurans with amine functionalities at the 2-position and alkyl groups at the 3-position. Cross-over experiments showed that the alkyl-migration step was an intermolecular process. X-ray crystal-structure analysis of two of the products supported our structural assignment. In some cases, the corresponding benzofurans without the alkyl group at the 3-position were obtained as side-products, which were formed through a competing protodeauration process.

From Ynamides to Highly Substituted Benzo[b]furans: Gold(I)‐Catalyzed 5‐endo‐dig‐Cyclization/Rearrangement of Alkylic Oxonium Intermediates

Fucoidans are marine sulfated biopolysaccharides that have heterogenous and complicated chemical structures. Various sugar monomers, glycosidic linkages, molecular masses, branching sites, and sulfate ester pattern and content are involved within their backbones. Additionally, sources, downstream processes, and geographical and seasonal factors show potential effects on fucoidan structural characteristics. These characteristics are documented to be highly related to fucoidan potential activities. Therefore, numerous chemical qualitative and quantitative determinations and structural elucidation methods are conducted to characterize fucoidans regarding their physicochemical and chemical features. Characterization of fucoidan polymers is considered a bottleneck for further biological and industrial applications. Consequently, the obtained results may be related to different activities, which could be improved afterward by further functional modifications. The current article highlights the different spectrometric and nonspectrometric methods applied for the characterization of native fucoidans, including degree of purity, sugar monomeric composition, sulfation pattern and content, molecular mass, and glycosidic linkages.

Fucoidan Characterization: Determination of Purity and Physicochemical and Chemical Properties

The gold-catalyzed conversion of allyl-(ortho-alkynylphenyl)methyl ethers was investigated, and allylated isochromenes were obtained. An optimization of the catalysis conditions with respect to different phosphane and carbene ligands on gold, different counterions, and different solvents was conducted. Subsequently, the scope and limitations of this reaction were investigated with 21 substrates. The mechanistic studies show an allylic inversion, as supported by NMR data and an X-ray crystal structure analysis, as well as an intermolecular reaction, as determined by crossover experiments. There is no competition of protodeauration even in the presence of water. All these observations differ from other related conversions and clearly indicate product formation by a [3,3]sigmatropic rearrangement in the step forming the new C-C bond.

[3,3]‐Sigmatropic Rearrangement Step in the Gold‐Catalyzed Cyclization of Allyl‐(ortho‐alkinylphenyl)methyl Ethers

Glycosaminoglycans are complex biomolecules of great biological and medical importance. The quantification of glycosaminoglycans, in particular in complex matrices, is challenging due to their inherent structural heterogeneity. Heparin Red, a polycationic, fluorescent perylene diimide derivative, has recently emerged as a commercial probe for the convenient detection of heparins by a mix-and-read fluorescence assay. The probe also detects glycosaminoglycans with a lower negative charge density than heparin, although with lower sensitivity. We describe here the synthesis and characterization of a structurally related molecular probe with a higher positive charge of +10 (vs. +8 of Heparin Red). The superior performance of this probe is exemplified by the quantification of low dermatan sulfate concentrations in an aqueous matrix (quantification limit 1 ng/mL) and the detection of dermatan sulfate in blood plasma in a clinically relevant concentration range. The potential applications of this probe include monitoring the blood levels of dermatan sulfate after administration as an antithrombotic drug in the absence of heparin and other glycosaminoglycans.

https://www.mdpi.com/1420-3049/22/5/768/pdf

A Fluorescent Probe for Glycosaminoglycans Applied to the Detection of Dermatan Sulfate by a Mix-and-Read Assay

The reaction proceeds via a gold-catalyzed cyclization step and [3,3]-sigmatropic rearrangement with formal inversion of the allylic moiety.

Melissa Rappold

Papers

[3,3]‐Sigmatropic Rearrangement Step in the Gold‐Catalyzed Cyclization of Allyl‐(ortho‐alkinylphenyl)methyl Ethers

A Fluorescent Probe for Glycosaminoglycans Applied to the Detection of Dermatan Sulfate by a Mix-and-Read Assay

[3,3]-Sigmatropic Rearrangement Step in the Gold-Catalyzed Cyclization of Allyl-(ortho-alkinylphenyl)methyl Ethers.