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.