Paul C. Young

Divergent outcomes of gold(I)-catalyzed indole additions to 3,3-disubstituted cyclopropenes.

Depending on the conditions employed, gold(I)-catalyzed addition of indoles to 3,3-disubstituted cyclopropenes can be controlled to yield either 3-(E)-vinylindoles (3) or bis-indolylalkanes (4). If the cyclopropene substituents are sterically bulky, unprecedented gold-catalyzed oxidation under air occurs to yield bis-indolylalkene (5) and epoxide (6) at room temperature.

Gold(I) and Palladium(II) Complexes of 1,3,4-Trisubstituted 1,2,3-Triazol-5-ylidene “Click” Carbenes: Systematic Study of the Electronic and Steric Influence on Catalytic Activity

The synthesis of a small family of six electronically and sterically modified 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene gold(I) chloride complexes is described. Additionally, the corresponding trans-[PdBr2(iPr2-bimy)(1,3,4-trisubstituted 1,2,3-triazol-5-ylidene)] complexes are also generated and used to examine the donor strength of the 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene ligands. All compounds have been characterized by 1H and 13C NMR and IR spectroscopy, high-resolution electrospray mass spectrometry (HR-ESI-MS), and elemental analysis. The molecular structures of four of the gold(I) and four of the palladium(II) complexes were determined using X-ray crystallography. Finally, it is demonstrated that these 1,2,3-triazol-5-ylidene gold(I) chloride complexes (Au(trz)Cl) are able to catalyze the cycloisomerization of 1,6-enynes, in high yield and regioselectivity, as well as the intermolecular direct etherification of allylic alcohols. Exploiting the Au(trz)Cl precatalysts allowed the etherification of allylic alcohols to be carried out under milder conditions, with better yield and regioselectivity than selected commercially available gold(I) catalysts.

Gold(I)-Catalyzed Addition of Thiols and Thioacids to 3,3-Disubstituted Cyclopropenes

Gold(I)-catalyzed reactions of thiols, thiophenols, and thioacids with 3,3-disubstituted cyclopropenes occur in a regioselective and chemoselective manner to produce either vinyl thioethers or primary allylic thioesters in good yields. A survey of commonly used gold(I) catalysts shows Echavarrens cationic gold(I) catalyst to be most tolerant of deactivation by sulfur. A novel digold with bridging thiolate complex is characterized by X-ray crystallography, shedding light on a possible deactivation pathway.

Deactivation of gold(I) catalysts in the presence of thiols and amines – characterisation and catalysis

Thiols and amines, which are common heteroatom nucleophiles in gold-catalysed reactions, are known to dampen the reactivity of gold catalysts. In this article, the identity and activity of gold(I) catalysts in the presence of thiols and amines is investigated. In the presence of thioacid, thiophenol and thiol, digold with bridging thiolate complexes [{Au(L)}2(μ-SR)][SbF6] are formed and have been fully characterised by NMR and X-ray crystallography. In the presence of amines and anilines, complexes [LAu-NH2R][SbF6] are formed instead. All new isolated gold complexes were investigated for their catalytic activity in order to compare the level of deactivation in each species.

Gold(I)-catalysed one-pot synthesis of chromans using allylic alcohols and phenols

Summary A gold(I)-catalysed reaction of allylic alcohols and phenols produces chromans regioselectively via a one-pot Friedel–Crafts allylation/intramolecular hydroalkoxylation sequence. The reaction is mild, practical and tolerant of a wide variety of substituents on the phenol.

Gold(I)‐Catalysed Direct Thioetherifications Using Allylic Alcohols: an Experimental and Computational Study

A gold(I)-catalysed direct thioetherification reaction between allylic alcohols and thiols is presented. The reaction is generally highly regioselective (SN2′). This dehydrative allylation procedure is very mild and atom economical, producing only water as the by-product and avoiding any unnecessary waste/steps associated with installing a leaving or activating group on the substrate. Computational studies are presented to gain insight into the mechanism of the reaction. Calculations indicate that the regioselectivity is under equilibrium control and is ultimately dictated by the thermodynamic stability of the products.

Chirality Transfer in Gold(I)‐Catalysed Direct Allylic Etherifications of Unactivated Alcohols: Experimental and Computational Study

Gold(I)-catalysed direct allylic etherifications have been successfully carried out with chirality transfer to yield enantioenriched, γ-substituted secondary allylic ethers. Our investigations include a full substrate-scope screen to ascertain substituent effects on the regioselectivity, stereoselectivity and efficiency of chirality transfer, as well as control experiments to elucidate the mechanistic subtleties of the chirality-transfer process. Crucially, addition of molecular sieves was found to be necessary to ensure efficient and general chirality transfer. Computational studies suggest that the efficiency of chirality transfer is linked to the aggregation of the alcohol nucleophile around the reactive π-bound Au–allylic ether complex. With a single alcohol nucleophile, a high degree of chirality transfer is predicted. However, if three alcohols are present, alternative proton transfer chain mechanisms that erode the efficiency of chirality transfer become competitive.