A smooth, gold catalyzed, atom‐economical and regioselective synthesis of indoles is reported here. The reaction occurs from a nucleophilic attack of in situ synthesized triazapentalenes to gold activated ynamides and involves the participation of α‐imino gold carbene complexes. The use of sulfonyl ynamides drives the reaction to the formation of 2‐amidosubstituted indoles. However, the employment of 2‐oxazolidinolylynamides allows the formation of both isomers, such as, 2‐amido‐ and 3‐amidosubstituted indoles. In this case, the regioselection could be controlled by a correct choice of the catalyst ligand and the electron‐donating capability of the aryl substituent of the ynamide. A correct control in both parameters permits a totally regioselective synthesis of one or the other regioisomer. Isolation of key intermediates and X‐ray analysis allowed for a plausible explanation for this behavior.

Here we report a gold(I)‐catalyzed and atom‐economical ortho‐N‐indolyl‐N‐pyrazolylbenzene synthesis from 1,2,3‐triazapentalenes and ynamides. The reaction occurs through the cleavage of the triazole ring and formation of a α‐imino gold carbene intermediate. An aza‐Nazarov‐type cyclization with participation of an arene ring is involved. The reaction consists in a formal [4+1] heterocycloaddition where the four‐carbon synthon is provided by the ynamide. Finally, indole synthesis could also be performed in a one‐pot procedure from their 1‐propargyl‐1H‐benzotrizaole precursors.

Here we report a gold(I)‐catalyzed rearrangement for a special type of alkynylcyclopropanes, such as (6‐ethynylbicyclo[3.1.0]hex‐2‐en‐6‐yl)silanes. These enynes evolved through an isomerization reaction towards the formation of isomeric alkynylcyclopropanes instead of the expected alkynylcyclohexadienes. A computational study on the reaction mechanism revealed the participation of a polycyclic gold(I) carbene complex as intermediate instead of a σ‐allylic gold cation which is in agreement with the expected influence in the energy of those intermediates due to the presence of the silyl group. Finally, this gold(I) carbene intermediate could be experimentally intercepted through intramolecular cyclopropanations.

A gold‐catalyzed bispropargylation of xanthone derivatives is described. The use of propargylsilanes permits to achieve a deoxygenative bispropargylation through a double catalytic addition of the corresponding allenylgold intermediate to the synergistically activated carbonyl moiety. This methodology works in a diastereoselective manner either with xanthone or thioxanthone derivatives. Monopropargylated xanthydrol silyl ethers were isolated as reaction intermediates and these species could be transformed into symmetrical and non‐symmetrical bispropargylated xanthenes. The formation of non‐symmetrical bispropargylated xanthenes could also be achieved through an one‐pot procedure. Finally, other interesting structures, such as propargylxanthylidenes, propargylxanthenes and bispropargylated xanthenes replacing the silicon moiety, were accessible following different one‐pot synthetic methodologies. In addition, bispropargylated xanthenes could perform a carbonylative [2+2+1] formal cycloaddition.