Sulfur-Based Ylides in Transition-Metal-Catalysed Processes

Abstract

Traditionally employed in the synthesis of small ring systems and rearrangement chemistry, sulfur-based ylides occupy a unique position in the toolbox of the synthetic organic chemist. In recent years a number of pioneering researchers have looked to expand the application of these unorthodox reagents through the use of transition metal catalysis. The strength and flexibility of such a combination have been shown to be of key importance in developing powerful novel methodologies. This chapter summarises recent developments in transition metal-catalysed sulfonium/sulfoxonium ylide reactions, as well as providing a historical perspective. In overviewing the successes in this area, the authors hope to encourage others into this growing field.

Recent advance in sulfur ylide and sulfonium salts chemistry

“…排反应引起了广泛关注 [11] . 在前人工作以及苯炔引 发 的 基 于 氮 叶 立 德 中 间 体 的 叔 胺 重 排 反 应 基 础 上 [12,13] , 本课题组 [14] 报道了一类苯炔引发的烯丙基 硫醚的 [2,3] 印度Biju课题组 [15] 以及重庆大学贺耘课题组 [16] [27] . 近年来, 基于金属卡宾和硫醚的重排反 应愈发引起了科学家的重视, 在不对称催化以及水 相合成等方面已有突破性的进展.…”

“…1997年, 埃默里大学Liebeskind课题组 [40] 报道了首例 利用五元环状硫鎓盐作为偶联反应底物, 参与钯或 镍催化的碳−碳偶联反应的工作. 在其后10年, 相关 研究并没有引起广泛关注, 直到近期才重新进入科 学家的视野 [27] .…”

Gold‐Catalyzed Oxidative Alkyne Functionalization by N−O/S−O/C−O Bond Oxidants

“…Both intermolecular and intramolecular approaches of alkyne oxidation offer excellent synthetic flexibility in carbenoid chemistry and the chemistry of alkyne oxidative functionalization has attracted wide attention of synthetic community for investigation on various modes of alkyne oxygenation and further applications. On the other hand, a rather similar type of transformations of gold activated alkynes with series of SÀ C/SÀ N bonded reagents like sulfur based ylides [18] specially sulfilimines, [19] variable nucleophilic nitrenoids, [20] and others [21] have been extensively studied where α-imino gold carbenes or others related species forms which can be exploited in versatile and powerful new organic transformations. However, in this review we have focused only on gold activated alkyne oxygenation where α-oxo gold carbenes/oxygenated alkenyl gold intermediates are invoked for oxidative alkyne functionalizations (Scheme 1).…”

Gold‐Catalyzed Cycloisomerization of Sulfur Ylides to Dihydrobenzothiepines

“…Six decades past the pioneering work of Johnson [1][2][3] and Corey, [4,5] sulfonium and sulfoxonium ylides have arguably become textbook reagents in organic synthesis. [6][7][8][9][10] In particular,t hey serve as one-carbon synthons for the construction of small rings such as epoxides, [11][12][13][14][15][16][17] cyclopropanes [11,[17][18][19][20] and aziridines [11,17,[20][21][22][23] as well as fort he synthesis of more complex cores through rearrangementr eactions. [24] Whilst the majority of the initial studies wereb ased on non-stabilized sulfonium and sulfoxonium ylides, modern work exploits the reactivityo f their stabilized surrogates, in which electron density from the ylidic carbon is distributed to one or two electron-withdrawing functionalities.…”