Based On Intramolecular 1,3-Dipolar Cycloaddition And Insertion Reaction Access To P,N,S-Containing Heterocyclic

Organophosphorus and organosulfurs compounds exist extensively in many drug molecules and natural compounds.These heterocycles are also the core of pharmaceutically relevant compounds.As a consequence,we are focus on developing simple and efficient methods to construct these molecules.In this paper,two strategies for construction of3,4-dihydrophosphocoumarin skeleton and 3-sulfenylated oxindoles skeleton have been reported through intramolecular 1,3-dipolar cycloaddition of nitrones and azomethine ylides as well as efficient S-H bond insertions of Kukhtin-Ramirez adducts,respectively.We have developed two methods for the construction of phosphocoumarin skeletons containing phosphine and nitrogen heterocycles by the intramolecular 1,3-dipolar cycloaddition involving o-vinylphosphonylated salicylaldehydes:?1?Constructing isoxazolidine-cis-fused phosphadihydrocoumarins skeleton by intramolecular 1,3-dipolar cycloaddition reaction of nitrone-vinylphosphonate dipole in a diastereoselective and catalyst-free manner?12 new compounds,80-90%yields?;?2?A high diastereoselective access to oxindole spiro-P,N-polycyclic heterocycles employing azomethine ylides generated in situ from the condensation of primary amines and o-vinylphosphonylated salicylaldehydes?28 new compounds,67-96%yields?;?3?Synthesis of 3-sulfenylated oxindoles by trivalent phosphorus-mediated Kukhtin-Ramirez reaction of thiol?phenol?compounds with isatins.This reaction adopt a unique pattern to realized S-H functionalization by a metal-free S-H insertion reaction?36 new compounds,51-89%yields?.In this paper,all new compounds were characterized by ¹H NMR,³¹P NMR,¹³C NMR,HMBC,HSQC,HRMS,X-Ray.The metal-free catalyzed,atom economy and mild conditions make this reaction valuable in synthetic chemistry.Those strategies are expected to potentially apply into the the synthesis of P,N,S heterocyclic-containing biologically active compounds and natural products.