转自：康龙化成

Photocatalyzed Dicyanation of Alkenes Enabled by Phosphorus Radical Cation Addition

Jing Li, Yanyan Zhang, Shengqing Zhu,*and Lingling Chu*

State Key Laboratory of Advanced Fiber Materials, College of Chemistry and Chemical Engineering, Center for Advanced Low-Dimension Materials, DonghuaUniversity, Shanghai 201620, China

—Chem. - Eur. J. 2025, DOI:10.1002/chem.202501154

Recommended by Xiaoyu Geng_PDM

KEYWORDS: Photo chemistry, Dicyanation (反应类型), C(sp)-C(sp3) (成键类型), Alkenes(原料), alkyl 1,2-dinitriles (产物),PPh3, phosphinephotoredox(其他)

ABSTRACT: While notable progress has been made in alkene cyanation for the synthesis of alkyl nitriles, catalytic strategies enabling the direct dicyanation of simple alkenes remain relatively underexplored. In this study, we introduce a synergistic phosphinephotoredox catalytic system that facilitates the direct dicyanation of styrenes using TMSCN in the presence of oxidant. This approach utilizes a phosphorus radical cation to initiate an oxidative radical-polar crossover with alkenes, followed by sequential nucleophilic cyanation. This protocol allows for the efficient synthesis of alkyl 1,2-dinitriles from alkenes under mild conditions. Notably, the method exhibits broad substrate scope and commendable efficiency, serving as a valuable complement to existing cyanation methodologies. The synthetic utility of the dinitrile products is further demonstrated through diverse derivatization reactions, highlighting their applicability in constructing nitrogen-rich molecular architectures. Mechanistic studies provide further insight into the reaction pathway and underscore the potential of phosphorus radical cations in alkene functionalization.

Dicyanation of alkenes via a merged organophosphine-photoredox catalysis

Substrate Scope

Synthetic Application: Derivatization of products and applications in the synthesis of complex molecules

Carboxylic acid is frequently found in drug molecules. To date, the synthesis of carboxylic acid involves alkali metal base medicated, transition metal catalyzed carbonylation, hydrolysis of ester, amide and cyanide. Prof. Chu group reported visible-light driven dicyanation of styrenes. This method tolerates phenyl, heterocyclic alkenes and gave modest to good yields. It is noteworthy that the product dicyanide can be hydrolyzed to give dicarboxylic acid, which can be used to synthesis of bioactive molecules. 

羧酸在药物分子中广泛存在。目前，合成方法有主族碱物种参与或金属催化的插羰基羧酸化反应，羧酸酯、酰胺或氰基水解。东华大学的储玲玲教授课题组报道了基于光催化的苯乙烯双氰基化反应，该反应兼容苯基或杂环取代的苯乙烯，收率中等到良好。产品二腈可以进一步水解生成二羧酸，该羧酸中间体可以被用来合成一系列药物分子。

（转自：康龙化成）