Ligand-Free Iron-Catalyzed Construction of C-P Bonds via Phosphorylation of Alcohols: Synthesis of Phosphine Oxides and Phosphine Compounds.

An efficient method for the construction of C-P(V) and C-P(III) bonds via the iron-catalyzed phosphorylation of alcohols under ligand-free conditions is disclosed. This strategy represents a straightforward process to prepare a series of phosphine oxides and phosphine compounds in good to excellent yields from the readily available alcohols and P-H compounds. A plausible mechanism is also proposed.

Synthesis of acyl fluorides through deoxyfluorination of carboxylic acids.

A direct deoxyfluorination of carboxylic acids by utilizing inorganic potassium fluoride (KF) as a safe and inexpensive fluoride source has been developed. Both aryl carboxylic acids and cinnamyl carboxylic acids could be efficiently transformed into valuable acyl fluorides in moderate to high yields with good functional group tolerance. A scale-up reaction could be carried out smoothly under solvent-free conditions, which further demonstrated the practicality of this reaction in organic synthesis.

Metal-free highly chemo-selective bisphosphorylation and deoxyphosphorylation of carboxylic acids.

Carboxylic acids are readily available in both the natural and synthetic world. Their direct utilization for preparing organophosphorus compounds would greatly benefit the development of organophosphorus chemistry. In this manuscript, we describe a novel and practical phosphorylating reaction under transition metal-free reaction conditions that can selectively convert carboxylic acids into the P-C-O-P motif-containing compounds through bisphosphorylation, and the benzyl phosphorus compounds through deoxyphosphorylation.