Radical Phosphination of Organic Halides and Thioates

Significance

Although the syntheses of organophosphines based on the reactions of phosphorus-centered radicals are rather common, this is one of the first methods for a substitution reaction giving aryl- and alkylphosphines via a radical pathway. This approach allows to obtain functionalized aryl diphenylphosphines from the corresponding aryl iodides as well as enantioenriched alkyldiarylphosphines from some chiral alcohols without need of highly basic conditions. For substrates with a properly placed C=C bond, a sequential cyclization-phosphination reaction was demonstrated. It can be predicted that this new and original method will find broad synthetic applications.