Novel 3H‐1,2,3‐Dithiaphosphole and Unprecedented 1,3,2,4‐Dithiadiphosphinane Heterocycles: Unanticipated Cyclization Reactions of Lawesson's Reagent and Alkynes
Year: 2025
Type: article
Abstract: The treatment of Lawesson's reagent with selected alkyl or aryl alkynes results in the formation of cyclization products such as 3H‐1,2,3‐dithiaphosphole‐3‐sulfide or unprecedented 1,3,2,4‐dithiadiphosphinane‐2,4‐disulfide derivatives. The new heterocycles are characterized spectroscopically and in two cases by crystal structure analyses. Density functional theory (DFT) computations (PW6B95D3/6‐311 + G(d,p)‐PCM(toluene)//B97D3/6‐31 G*) explain the formation of the dithiaphosphole product from alkynes and Lawesson's reagent via a sequence of [2 + 2] addition, electrocyclic ring opening, SS bond forming ring closure, and P(III) oxidation by sulfur transfer from Lawesson's reagent. Based on DFT calculations, the formation of a 1,3,2,4‐dithiadiphosphinane‐2,4‐disulfide is rationalized by a sequence of cyclization, electrocyclic ring opening, and dipolar cyclization steps.
Authors: Felix Blüm, Bernd Goldfuss, Holger Butenschön
Institutions: Leibniz University Hannover, University of Cologne
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,330
OpenAlex ID: W4409903785