Gold(iii)-arene complexes by insertion of olefins into gold-aryl bonds.

Gold(iii)–arene complexes by insertion of olefins into gold–aryl bonds† †Electronic supplementary information (ESI) available: Experimental details (syntheses, analytical data and copies of 1H, 13C and 31P NMR spectra), crystallographic data of 2 and computational details. CCDC 1526613 and 1538015. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00145b Click here for additional data file. Click here for additional data file.

Stoichiometric to catalytic reactivity of the aryl cycloaurated species with arylboronic acids: insight into the mechanism of gold-catalyzed oxidative C(sp2)-H arylation.

Based on the well-defined five-membered aryl gold(iii) complexes, [Au(tpy)X2] (3a and 3b) and [AuBr(Ph)(tpy)] (7), as well as the aryl gold(iii) complex [AuCl2(Ph)(tpy)] (8) (tpy = 2-(o-tolyl)pyridine) as reliable models, we present a detailed study of the mechanism for gold(iii)-catalyzed oxidative cross-coupling reactions between cycloaurable arenes and arylboronic acids. Here we report the d...

Efficient functionalization of aromatic C-H bonds catalyzed by gold(III) under mild and solvent-free conditions.

A gold(III)-catalyzed carbon-carbon bond formation reaction between arenes and electron-deficient alkynes or alkenes is described. Electron-rich arenes can be efficiently functionalized with the alkyne or alkene substrates. This reaction can be run with neat reactants at ambient temperature. Under the "solventless" conditions, clean product was obtained from a reaction of equal molar amounts of...

Regioselective Heck reaction of aliphatic olefins and aryl halides.

A regioselective Heck reaction of aliphatic olefins and aryl bromides is realized at internal carbons of olefins. Methanol solvent promoted halide ionization from neutral arylpalladium halide complexes via hydrogen bonding, so as to create cationic aryl-Pd species for regioselective olefin insertion.

Migratory Insertion of Carbenes into Au(III)–C Bonds

Migratory insertion of carbon-based species into transition-metal-carbon bonds is a mechanistic manifold of vast significance: it underlies the Fischer-Tropsch process, Mizoroki-Heck reaction, Ziegler-Natta and analogous late-transition-metal-catalyzed olefin polymerizations, and a number of carbonylative methods for the synthesis of ketones and esters, among others. Although this type of react...