A gold-catalyzed post-Ugi ipso-cyclization for the diastereoselective synthesis of spirocyclic pyrrol-2-one-dienone system is described. Tuning the catalytic system, solvent, and temperature allowed selectively attaining two sets of diastereoisomers. The scope of the process has been evaluated, and a putative mechanistic model was proposed.

A silver(I) triflate‐catalyzed protocol for the post‐Ugi synthesis of tetracyclic spiroindolines has been developed. The protocol worked best for indole‐3‐carbaldehyde‐derived Ugi adducts obtained using anilines and 3‐aryl propiolic acids. Thus, it is complementary to the previous cationic gold‐catalyzed procedure that was developed for analogues Ugi substrates derived from aliphatic amines and 3‐alkyl propiolic acids. Furthermore, we have demonstrated that under our new settings this domino Friedel‐Crafts ipso cyclization / imine trapping process could be efficiently combined with the preceding four‐component Ugi reaction into a two‐step one‐pot transformation.

A gold‐catalyzed post‐Ugi cascade transformation for the synthesis of 2‐pyridones is described. The process involves furan–alkyne cyclization followed by furan ring‐opening and cleavage of the isocyanide‐originated fragment. The initially formed cis double bond can isomerize into a more stable trans double bond upon prolonged exposure to a strong Brønsted acid. Thus, the overall strategy provides a viable access towards two types of 2‐pyridones.

In this report, we introduce a new strategy for controlling the stereochemistry in Ugi adducts. Instead of controlling stereochemistry directly during the Ugi reaction we have attempted to stereodefine the chiral center at the peptidyl position through the post-Ugi functionalization. In order to achieve this, we chose to study 2-oxo-aldehyde-derived Ugi adducts many of which partially or fully exist in the enol form that lacks the aforementioned chiral center. This in turn led to their increased nucleophilicity as compared to the standard Ugi adducts. As such, the stereocenter at the peptidyl position could be installed and stereodefined through the reaction with a suitable electrophile. Towards this end, we were able to deploy an asymmetric cinchona alkaloid-promoted electrophilic fluorination producing enantioenriched post-Ugi adducts fluorinated at the peptidyl position.

A four‐component one‐pot transformation involving the Passerini reaction, an aldol addition, and a transesterification has been elaborated, providing an access to a library of densely functionalized tartaric acid derivatives. Two modifications of the process have been explored. In the first modification, carboxylic acids and isocyanides were treated with an excess of ethyl glyoxalate leading to the incorporation of two ethyl glyoxalate residues in the resulting post‐Passerini products. The second modification involved the initial reaction of a carboxylic acid, an aryl glyoxal and an isocyanide to form the Passerini adduct. This was followed by the in situ addition of ethyl glyoxalate to produce the second type of post‐Passerini products through aldol addition and transesterification.