Metal-free hydrodifunctionalization of enaminones for the synthesis of ketomethylene-functionalized phosphoryl alcohols.

Reported here is a set of three-component reactions of enaminones with diaryl phosphine oxides and water for the synthesis of ketomethylene-functionalized -phosphoryl alcohols enaminone hydrodifunctionalization, enabling the cascade construction of new C-P, C-O and C-H bonds. The method displays notable advantages including mild metal-free conditions, a broad application scope and being free of the need to carry out chromatographic purification.

Tunable vicinal, geminal diphosphorylation and C-N bond phosphorylation of enaminones toward divergent phosphorylated ketone derivatives.

This paper reports the trifunctionalization reactions of tertiary enaminones in the fashion of selective - and vicinal diphosphorylation, leading to the tunable synthesis of α,α- and α,β-diphosphoryl ketones. In addition, the C-N bond phosphorylation with improved substrate tolerance has been achieved.

Acyl Cyanides as Bifunctional Reagent: Application in Copper-Catalyzed Cyanoamidation and Cyanoesterification Reaction.

Cu-catalyzed domino decyanation and cyanation reaction of acyl cyanides with amines or alcohols have been developed. The cyano sources were generated in situ via C-CN cleavage yielding the corresponding cyano substituted amides or esters in moderate to excellent yields. This approach features a cheap copper catalyst, domino decyanation and cyanation reaction, readily available starting materials, broad substrate scope, operational simplicity, and the potential for further transformation of the cyano group.