Metal-catalyzed divergent synthesis from ylides with 3-arylbenzo[][1,2,3]triazin-4(3)-ones.

The present work reveals a new metal-catalyzed synthetic reaction involving 1,2,3-benzotriazinones with carbonyl sulfoxonium ylide and iodonium ylide, resulting in divergent products. Within this catalytic system, 3-phenylbenzo[][1,2,3]triazin-4(3)-one derivatives undergo C-H alkylation processes facilitated by a Cp*Rh(III) catalyst when combined with a carbonyl sulfoxonium ylide. On the other hand, when iodonium ylide substrates are used, they undergo an alkenylation reaction facilitated by a Cp*Ir(III) catalyst.

Isocyanide-Based Multicomponent Reaction: Cascade α-Acyloxylation/Carboxamidation and [3 + 1+1] Cyclization of I/S-Ylides.

A metal-free cascade of α-acyloxylation/carboxamidation of I/S-ylides, carboxylic acids, and isonitriles via a Passerini-like multicomponent reaction is reported. Unexpectedly, [3 + 1+1] cyclization involving I/S-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.

A Platform for the Synthesis of Diverse Phosphonyl and Thiofunctionalized Sulfoxonium Ylides.

A practical strategy for the construction of diverse phosphonyl and thiofunctionalized sulfoxonium ylides via controllable monofunctionalization of hybrid I/S ylides is presented. This process allows efficient P-H insertion of I/S ylides under Cu catalysis, enabling the synthesis of phosphonyl sulfoxonium ylides, whereas reaction with sulfur-containing reagents including AgSCF, 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.

Cp*Rh(III)-Catalyzed ortho-Alkylation/Alkenylation of Nitroarenes.

Cp*Rh(III)-catalyzed nitro-directed C-H alkylation/alkenylation of nitroarenes has been reported for the first time. This protocol is associated with the features of high efficiency, broad substrate scope, and good functional group compatibility. Additionally, gram-scale experiments and synthetic applications proved the practicability of the method.