Addition, Reduction, and Oxidation Reactions of Nitrosobenzene

Reaction of Arylnitroso Derivatives: Synthesis of Arylimino 2,5-Dihydrofuran and Arylamino Fulvenes Derivatives

“…Finally, the hydrolysis (the reaction is made in non-anhydrous conditions) of the trifluoroacetamidate group gave the observed compounds 3a-d. The formation of the imines 6a-d and nitrones 5a-d could be explained by an Ehrlich-Sachs condensation mechanism involving nitroso group and acidic methyl group, followed by partial oxidation to 5 by the excess of reagent [3].…”

“…The formation of fulvenes can be hypothesized as deriving from 6a-d considering that nitrosobenzene, in presence of carbanions with good leaving groups gave N-oxides [3]. In this case, the acidic NH was deprotonated to an N-anion able to carry a nucleophilic attack to the electrophilic nitrosoaniline.…”

“…As an expansion of this study, we focused on arylnitroso derivatives as potential reagents for cyclopentadiene 1. Arylnitroso species were shown to give numerous reactions with unsaturated molecules, including cycloadditions and Aldol Michael [3]- [9]. In this context, the formation of 1,2-oxazines would be of wide importance, due to the possibility of further chemical elaboration of this structure to access important scaffolds [10].…”

Research Progress on Nitroso-ene Reaction

“…亚硝基化合物是一类具有高活性的反应中间体, 能 够进行多种反应从而得到不同含有氮氧官能团化的产 物 [5,6] . 例如亚硝基化合物可以通过杂 Diels-Alder 反 应 [7] 、Aldol 加成反应 [8] 以及 ene 反应 [9] 等来分别得到含 有 δ-氨基醇、烯丙基胺、羰基 α 位氨化或羟胺化等在药 物分子和天然产物中常见的结构单元, 同时它们还是有 机合成化学中极为重要的中间体 [10] .…”

“…含有亚硝基官能团的化合物通常具有很强的亲电 性质, 可以进行一系列的反应, 如加成反应、异构化、 氧化及还原反应 [5,6] . 从 Scheme 1 中可以看出, 作为亲 电 试 剂 , 它 能 够 与 烯 醇 化 物 [11] 物 [12] (路线 b)和格氏试剂 [13] (路线 c)发生加成反应.…”