Search

A metal-free cascade of α-acyloxylation/carboxamidation of I (III) /S (VI) -ylides, carboxylic acids, and isonitriles via a Passerini-like multicomponent reaction is reported. Unexpectedly, [3 + 1+1] cyclization involving I (III) /S (VI) -ylides and two molecules of ethyl isocyanoacetate was observed. The strategy allows for the synthesis of unsymmetrical α,α-disubstituted ketones and functionalized pyrroles with up to 99% yield and wide substrate compatibility. Notably, the procedure has been extended to the late-stage modification of drugs and natural products, offering an elegant complement to the classic Passerini reaction.

A practical strategy for the construction of diverse phosphonyl and thiofunctionalized sulfoxonium ylides via controllable monofunctionalization of hybrid I (III) /S (VI) ylides is presented. This process allows efficient P-H insertion of I (III) /S (VI) ylides under Cu catalysis, enabling the synthesis of phosphonyl sulfoxonium ylides, whereas reaction with sulfur-containing reagents including AgSCF 3 , KSC(S)OR, and KSCN under mild conditions resulted in α-trifluoromethylthiolation, dithiocarbanation, and thiocyanation of sulfoxonium ylides accordingly. Of note, wide substrate compatibility (108 examples), excellent efficiency (up to 99% yield), gram-scale experiments, and various product derivatizations highlight the synthetic utility of this protocol.

Rh (III)-catalyzed dienylation and cyclopropylation of 1,2,3-benzotriazinones with alkylidenecyclopropanes (ACPs) has been achieved. Different from the previous reports of 1,2,3-benzotriazinones, the triazinone ring remained intact in this C-H bond functionlization reaction. Also, the denitrogenative cyclopropylation could also be realized by changing the reaction temperature. This protocol is featured with high E selectivity, wide substrate scope, and divergent structures of products.

Two categories of tetrasubstituted phenols were prepared via the cycloaddition reaction of vinyl sulfoxonnium ylides with cyclopropenones in a switchable manner. Copper carbenoid was proposed as the active intermediate in the process of 2,3,4,5-tetrasubstituted phenols formation, while 2,3,5,6-tetrasubstituted phenols were generated via the direct [3 + 3] annulation of vinyl sulfoxonnium ylides with cyclopropenones under metal-free conditions. Further synthetic applications were also demonstrated.