One-Pot Three-Component Condensation Synthesis and Structural Features of Organophosphorus-Sulfur Macrocycles

A new preparative route was developed to synthesize new phosphorus-sulfur [SP(═S)S moiety]-containing macrocycles via a one-pot and three-component domino reaction of four-membered ring thionation reagents such as 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide (LR, Lawesson's reagent) and 2,4-diferrocenyl-1,3,2,4-diathiadiphosphetane 2,4-disulfide (FcLR, a ferrocene analogue of Lawesson's reagent) and alkyldithiols(aryldithols) and dihaloalkanes in the presence of sodium hydride. Therefore, a series of 12- to 18-membered macrocycles incorporating two phosphorus and six sulfur atoms were synthesized. The synthesis features a novel application of the multicomponent reaction, providing an efficient route to the preparation of the new phosphorus-sulfur-containing macrocycles. Seven representative X-ray structures confirm the formation of these macrocycles and show the presence of a number of the intramolecular C-H···S hydrogen bonding, intermolecular C-H···S, C-H···Cl, and Cl···Cl short contacts and π-stacking interactions in their 3D network structures.