Phosphorus-centered Radicals Induced Bifunctionalization Of Alkynes

Organophosphorus compounds are important intermediates widely used in fields such as pesticides,pharmaceutical chemistry,functional materials,and coordination chemistry.In recent years,the use of phosphorus-centered radicals for the construction of C-P bonds has become an attractive topic in organic synthesis.Synthetic chemists have successively developed new strategies for the preparation of organophosporus compounds.From a green and economic standpoint,it is of great significance to achieve the efficient synthesis of this class of compounds in one reaction step.In this thesis,the phosphinyl radical initiated bifunctionalization reaction of alkynes was studied and a series of new and important phosphorus-containing organic compounds were synthesized.This thesis has been divided mainly into three parts as described below:1.In the first part,the phosphonation-thiocyanation reaction of alkynes was explored for the first time,affording ?-thiocyanoalkenyl phosphonates.The crystal structure of the compound was determined by XRD technique.On this basis,a series of ?-thiocyanoalken ylphosphonates were successfully synthesized.2.The second part focuses on the phosphorus radical-induced phosphonationchlorination(bromination)reaction of alkynes.A series of ?-chloro(?-bromo)alkenyl phosphonates were successfully synthesized.The structures of all synthesized products were identified by 1H,13 C,31P NMR and HRMS spectroscopic techniques.Based on the experimental results,a reasonable mechanism was proposed for these new reactions.