Three-Component Direct Phosphorylation of Aldehydes and Alkylation of Ketones: Synthesis of γ-Ketophosphine Oxides under Acidic Conditions.

An effective and economical acid-promoted three-component reaction for the construction of C-P and C-C bonds for the synthesis of γ-ketophosphine oxides with water as the only byproduct was developed. Detailed mechanistic experiments confirmed that the reaction proceeds by phospha-aldol elimination, in which a benzylic carbocation is generated from the phosphorylation of aldehydes, which then reacts with ketone enolates under acidic conditions.

Lewis Acid Enables Ketone Phosphorylation to Form a C-P Bond and a C-C Bond: Synthesis of 9-Phosphoryl Fluorene Derivatives.

An efficient method for the Lewis acid promotion of the synthesis 9-phosphoryl fluorenes has been reported. This method focuses on ketone phosphonylation to form a C-P bond and a C-C bond between diphenylmethanone and H-phosphinate esters, H-phosphites, and H-phosphine oxides via phospha-aldol elimination, in which a series of 9-phosphoryl fluorene derivatives were selectively obtained in moderate to excellent yields.