Sulfoxonium Ylide Derived Metal Carbenoids in Organic Synthesis

Abstract

As pioneered by Corey and Chaykovsky, sulfoxonium ylides have had widespread application in organic synthesis for more than a half century. In most of the reactions, sulfoxonium ylides were used to react with electrophiles. Under suitable reaction conditions these ylides can generate metal carbenoids and react with nucleophiles. By combining the typical reactivity of sulfoxonium ylides with transition-metal catalysis, a growing number of investigations have expanded their application in organic synthesis. This review provides an update on the preparation of sulfoxonium ylides and their applications in carbenoid transfer reactions.1 Introduction2 Preparation of Sulfoxonium Ylides3 Investigation for Carbenoid Formation from Sulfoxonium Ylide 4 X–H (X = N, O, S, C) Functionalization Reactions5 Polymerizaton of Carbenoids Generated from Sulfoxonium Ylides6 Conclusion and Perspective

Iridium‐Catalyzed [4+2] Annulations of β‐Keto Sulfoxonium Ylides and o‐Phenylenediamines: Mild and Facile Synthesis of Quinoxaline Derivatives

“…Since first β‐keto sulfoxonium ylides have been reported by the Chaykovsky group reported in the 1960s, this reagent has been increasingly popular as an important building block in organic synthesis . These ylides are well‐behaved and generally crystalline and bench‐stable solids, and can be easily prepared in one step from the corresponding carboxylic acids or their derivatives.…”

Visible Light‐Promoted Sulfoxonium Ylides Synthesis from Aryl Diazoacetates and Sulfoxides

“…Sulfoxonium ylides, one categories of sulfur ylides, [ 1 ] have been investigated as one of the most important synthons in synthetic organic chemistry. [ 2 ] Generally, sulfoxonium ylides are considered as alternative metal‐carbene surrogates due to their operational safety and synthetic convenience compared with structurally similar diazo compounds. Up to now, they have been used in numerous types of important organic transformations, including X—H insertion, cyclopropanation, epoxidation, aziridination, dimerizations, Wolff rearrangements, Stevens rearrangements and others.…”

Palladium-Catalyzed Synthesis of α-Carbonyl-α′-(hetero)aryl Sulfoxonium Ylides: Scope and Insight into the Mechanism

“…Whereas primary (3)(4)(5)(6) and secondary (7, 8) alkyl groups were compatible, attempts for which the R group was a tertiary alkyl group (e.g. adamantyl) led to no conversion.…”