Studies On Selective Phosphorylation Of Allylamine Derivatives Controlled By Nucleophiles

Phosphonate compounds and their derivatives play an important role in pesticides,plastics,printings and chemical materials,etc.In addition,organophosphorus compounds are important organic synthesis intermediates and ligands,so they have important application in flame retardants as well as materials and medicinal chemistry.Natural phosphonate compounds are mainly extracted from egg yolk and soybean,and exist as mainly lecithin.Meanwhile,organic synthesized phosphate esters have advantages such diversity of structure and function,easier degradation by organisms,lower irritation,and lower costs.Therefore,economical and environment friendly methods with high efficience for synthesis of phosphate esters have become more and more popular among by chemistry researchers.Herein,several studies have been carried out on the synthesis of phosphonates.The monophosphorylation and bisphosphorylation of allylamine derivatives were synthesized in a catalyst-free system.In the absence of catalysts and oxidants,C-P bond were constructed by the reaction of allylamine derivatives containing carbonyl groups with diethyl phosphites in DCE acompainied by the C-N bond cleavaging.In the same condition,when diphenylphosphine oxide was used instead of diethyl phosphite as a nucleophile,a Michael addition reaction of the diphenylphosphine oxide with the monophosphonation product which was given by the C-N bond cleavaging to obtain bisphosphorylated product in a high yields.Inspired by this,we treated diphenylphosphine oxide to the mono-phosphorylation products to synthesize an asymmetrical di-phosphorylation product.In this reaction system,Not only does it achieve a C-N bond cleavage in the absence of catalyst,but also bisphosphate products were obtained when diphenylphosphine oxides were used as nucleophiles to attack the carbon-carbon double bond.The reaction has good applicability of substrates and excellent yield,which meets the purpose of green chemistry.Lewis acids promote the synthesis of bisphosphonate compounds of allylamine derivatives.Using Fe?NO₃?₃·9H₂O as promoter,allylamine derivatives and trialkyl phosphites in DCE as solvent,highly efficiency and highly selectivity bisphosphorylation was obtained.Asymmetric bisphosphonate compounds can also be obtained by a one-pot reaction.The reaction avoids using noble metal as catalyst,the applicability is better and the target products can be obtained with high yields.