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Tunable Trifunctionalization of Tertiary Enaminones for the Regioselective and Metal-Free Synthesis of Discrete and Proximal Phosphoryl Nitriles

Zhongrong Xu, Leiqing Fu, Xia Fang, Bin Huang, Liyun Zhou, Jie‐Ping Wan

2021Organic Letters34 citationsDOI

Abstract

This paper reports an unprecedented trifunctionalization of tertiary enaminones for the synthesis phosphoryl nitriles by the reactions of enaminones with diarylphosphine oxides and trimethylsilyl cyanide (TMSCN) without the use of any metal reagent. Employing tetrabutyl ammonium hydroxide (TBAH) as the catalyst (0.2 equiv) enables discrete cyanophosphonation. On the other hand, selective proximal cyanophosphonation has been realized in the presence of acetic acid only (AcOH).

Topics & Concepts

ChemistryTrimethylsilyl cyanideRegioselectivityReagentCyanideTrimethylsilylAmmonium hydroxideAcetic acidHydroxideNitrileCombinatorial chemistryCatalysisAmmoniumMetalTetrabutylammonium hydroxideOrganic chemistryCatalytic C–H Functionalization MethodsSynthesis and Catalytic ReactionsSulfur-Based Synthesis Techniques
Tunable Trifunctionalization of Tertiary Enaminones for the Regioselective and Metal-Free Synthesis of Discrete and Proximal Phosphoryl Nitriles | Litcius