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

Abstract

Sulfoxonium ylides | Synthetic methods | Carbene | Visible Light | Diazo compoundsA visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetically useful sulfoxonium ylides was reported. The reaction occurred under sole visible light irradiation without the need of any transition-metals or additives, affording the corresponding sulfoxonium ylides in moderate to good yields. The success of late-stage modification of natural isolates or drug candidates, scale-up reaction and transformation of sulfoxonium ylides to other useful molecules further rendered the approach valuable.

Visible Light-Promoted Transformation of Diazo Compounds via the Formation of Free Carbene as Key Intermediate

“…昆明理工大 学江玉波、 肖铁波团队 [34] 亚砜叶立德作为一种高效的 C1 合成子, 广泛应用 于多种重要的有机转化过程中, 同时关于硫叶立德合成 方法学的研究也颇受关注 [35] . 近期, 我们课题组 [36] 报道 了可见光促进的芳基重氮酯与亚砜 56 的反应来构建一 系列亚砜叶立德产物 57 (Scheme 16). 该反应只需使用 可见光进行照射, 不需要任何催化剂以及添加剂就能以 中等至良好的收率获得目标产物 57, 同时该策略也表 现出了良好的官能团耐受性.…”

Asymmetric transformations from sulfoxonium ylides

“…The use of visible light (blue LED) instead of UV radiation proved to be very efficient. 121,122 In addition, catalytic amounts of copper powder or rhodium complexes were employed, reducing the amount of metal catalyst to promote the reaction. 38,123 Diazo substrates containing donor–acceptor and acceptor–acceptor substituents, with acceptor = carbonyl and donor = aryl, are well tolerated by this strategy and the products are provided in high yields.…”

Photocatalytic Transition‐Metal‐Free Direct 3‐Acetalation of Quinoxaline‐2(1H)‐ones

“…Recently, visible‐light‐promoted synthesis has emerged as a sustainable strategy for the direct derivatization of functionalized molecules. [ 25 ] The elegant works of Melchiorre's and Wang's group demonstrated that glyoxylic acid acetal could be converted into the formyl radical equivalent in photocatalyzed reaction systems. [ 26 ] Soon afterward, Xu's group reported an Ir‐photoredox‐ catalyzed addition of this formyl equivalent with various Michael acceptors.…”