Gold(I)-catalyzed highly regioselective hydration of alkynylsulfones comprises an efficient 100% atom-economic route to β-ketosulfones. The reaction proceeds under mild mercury-free conditions (Ph3PAuNTf2 0.5–5 mol %, THF, rt or 60 °С),...

The developed modular approach to hard-to-reach non-aromatic 3H- and 2H-pyrroles is based on the integration of 2H-azirines and ynamides. Gold-catalyzed [3+2] cycloaddition of 2,2-disubstituted 2H-azirines and ynamides comprises a high...

Gold­(I)-catalyzed [4 + 2] cycloaddition of indolylynamides and cyanamides (aminonitriles) is an efficient redox-neutral and atom-economic route to diversely substituted 1,3-diamino-β-carbolines. The protocol operates under mild conditions (Ph3PAuNTf2 5 mol %, DCE, 60 °C) with a good tolerance to functional groups (23 examples and yields up to 98%). The obtained β-carboline systems represent a versatile synthetic platform with modifiable substituents for successive functionalizations. Control experiments indicate the crucial role of both the nature of reactants and the identity of employed catalysts in the developed cycloaddition.

The gold-catalyzed annulation of alkynylsulfones, involving pyridine N-oxides (as O-atom transfer reagents) and nitriles (as C=N synthons), comprises a diazo-free route to valuable 4-sulfonyl-1,3-oxazoles. This reaction operates under relatively mild conditions (IPrAuNTf 2 5 mol %, rt or 60 °C), and a number of functionalities was compatible (35 examples; 14-95%). In most cases, the SO 2 fragment, which is typically expulsed in the previously reported Au-catalyzed O-transfers to alkynylsulfones, retains in the heterocyclic products. The postulated reaction mechanism suggests a key role of reactive gold α-oxo carbene intermediates formed via the O-atom transfer.