Rh(III)-Catalyzed Reaction of α-Carbonyl Sulfoxonium Ylides and Alkenes: Synthesis of Indanones via [4 + 1] Cycloaddition

Abstract

The synthesis of indanone derivatives by the Rh­(III)-catalyzed reaction of α-carbonyl sulfoxonium ylides with activated alkenes is reported. The reaction shows a high tolerance for functional groups and furnishes a variety of substituted indanone derivatives via a formal [4 + 1] cycloaddition. Highly stable sulfoxonium ylides were used as substrates in this C–H functionalization, and their bifunctional character could be effectively exploited using Rh­(III) catalysis via sequential double C–C bond formation. Based on mechanistic studies including deuterium-labeling experiments, the reaction is proposed to proceed as follows: Rh­(III)-catalyzed C–H oxidative alkenylation via β-hydride elimination, readdition of H–Rh species, a 1,2-carbon shift with the elimination of DMSO, and protonation.

Recent Advances in Metal‐Catalyzed C−H Bond Functionalization Reactions of Sulfoxonium Ylides

“…[36b] In 2020, Chatani and co-workers developed an oxidative Rh(III)-catalyzed CÀ H alkenylation of sulfoxonium ylides by [4 + 1] annulation with alkene for the construction of indanone derivatives via CÀ H activation, alkene insertion, β-hydride elimination, followed by RhÀ H reinsertion to C=C bond with subsequent DMSO elimination, 1,2-carbon shift and finally protonolysis with the help of solvent HFIP (Scheme 32). [37] A similar tandem reaction involving [4 + 1] annulative CÀ H functionalization of sulfoxonium ylides with acylates, styrene and acrylamides by cationic Rh(III) catalytic system was reported by Prabhu et al ( Scheme 33). [38] Scheme 29.…”

Metal-Free Chemoselective Reaction of Sulfoxonium Ylides and Thiosulfonates: Diverse Synthesis of 1,4-Diketones, Aryl Sulfursulfoxonium Ylides, and β-Keto Thiosulfones Derivatives

“…It is considered an important alternative to diazo compounds for its high reactivity. In recent years, the use of sulfoxonium ylides as the C1 or C2 synthons under the catalysis of transition metals (such as rhodium, ruthenium, cobalt, palladium, iridium, and other metals) has successfully achieved the activation of sp 2 C–H bonds of aryl groups and the synthesis of various heterocyclic compounds such as furan, indole, quinoline, pyrrole, and pyrimidine . In 2019, Xu’s group reported the reaction of sulfoxonium ylides with diazo compounds to prepare highly functionalized hydrazone compounds (Figure , eq 1) .…”

Asymmetric transformations from sulfoxonium ylides

“…26,27 From the products provided in the C-H activation step, many post functionalization reactions can be performed to generate structurally diverse heterocycles and carbocycles (Scheme 2F and G). [28][29][30][31][32][33][34][35][36] Important progress has also been made with regards to metal or carbenefree reactions by exploring the potential nucleophilicity of the sulfoxonium ylides. Some representative examples are the insertion reactions, [37][38][39] a-halogenations, 40 alkylations, 41 cyclizations, [42][43][44][45] ring CH 2 -homologations and epoxide ring opening reactions (Scheme 2H-L).…”