Herein we report a mild and diastereoselective access to ketonitrones by reacting easily available aryl acetic acid esters and other active methylene compounds, with nitrosoarenes under catalytic loading of 2‐tert‐butylimino‐2‐diethylamino‐1,3‐dimethylperhydro‐1,3,2‐diazaphosphorine (BEMP) at room temperature. Depending on the substitution pattern and nature of the aryl moiety, a switch toward the formation of imines can be observed. The mechanistic framework is put to scrutiny by experimental and theoretical studies, pointing to the formation of a nitroso aldol intermediate, whose fate toward one of the competing pathways, namely hydride transfer or elimination, would depend upon the NOH/CH_α relative acidities.

中文翻译：

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芳基乙酸酯与亚硝基芳烃的碱催化反应中的氮/亚胺选择性开关：联合实验和计算研究

在此，我们报告了在2-叔丁基亚氨基-2-二乙基氨基-1,3-二甲基过氢-1,3，室温下使用2-重氮磷（BEMP）。取决于取代模式和芳基部分的性质，可以观察到向亚胺形成的转换。在机械框架由实验和理论研究投入推敲，指向形成亚硝基羟醛中间体，其命运朝向竞争性途径，即氢化物转移或消除一个，将取决于NOH / CH _α相对酸度。