Details
| Original language | English |
|---|---|
| Article number | e202500219 |
| Journal | European Journal of Organic Chemistry |
| Volume | 28 |
| Issue number | 29 |
| Early online date | 29 Apr 2025 |
| Publication status | Published - 20 Aug 2025 |
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, S-S 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.
Keywords
- 1,2,3-dithiaphosphole-3-sulfides, 1,3,2,4-dithiaphosphinane, 1,3H-2,1,3-thiadiphosphole-1,3-disulfides, alkynes, Lawesson's reagent
ASJC Scopus subject areas
- Chemistry(all)
- Physical and Theoretical Chemistry
- Chemistry(all)
- Organic Chemistry
Cite this
- Standard
- Harvard
- Apa
- Vancouver
- BibTeX
- RIS
In: European Journal of Organic Chemistry, Vol. 28, No. 29, e202500219, 20.08.2025.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Novel 3H-1,2,3-Dithiaphosphole and Unprecedented 1,3,2,4-Dithiadiphosphinane Heterocycles
T2 - Unanticipated Cyclization Reactions of Lawesson's Reagent and Alkynes
AU - Blüm, Felix
AU - Goldfuss, Bernd
AU - Butenschön, Holger
N1 - Publisher Copyright: © 2025 The Author(s). European Journal of Organic Chemistry published by Wiley-VCH GmbH.
PY - 2025/8/20
Y1 - 2025/8/20
N2 - 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, S-S 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.
AB - 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, S-S 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.
KW - 1,2,3-dithiaphosphole-3-sulfides
KW - 1,3,2,4-dithiaphosphinane
KW - 1,3H-2,1,3-thiadiphosphole-1,3-disulfides
KW - alkynes
KW - Lawesson's reagent
UR - http://www.scopus.com/inward/record.url?scp=105011189956&partnerID=8YFLogxK
U2 - 10.1002/ejoc.202500219
DO - 10.1002/ejoc.202500219
M3 - Article
AN - SCOPUS:105011189956
VL - 28
JO - European Journal of Organic Chemistry
JF - European Journal of Organic Chemistry
SN - 1434-193X
IS - 29
M1 - e202500219
ER -