Attempts to Synthesize a Thiirane, Selenirane, and Thiirene by Dealkylation of Chalcogeniranium and Thiirenium Salts

Overview

Journal Chemistry

Specialty Chemistry

Date 2020 Aug 2

PMID 32737908

Citations 1

Authors

Helmut Poleschner

Konrad Seppelt

Affiliations

Soon will be listed here.

Abstract

Thiiranium salts [Ad SR] X (5, 8, 9, 11, 12; X =Tf N (Tf=CF SO ), SbCl ) and seleniranium salts [Ad SeR] X (14, 16, 17, 23-25; X =Tf N , BF , CHB Cl , SbCl ) are synthesized from strained alkene bis(adamantylidene) (1). The disulfides and the diselenides (Me SiCH CH E) (4, 13), (tBuMe SiCH CH E) (7, 22), and (NCCH CH E) (10, 15; E=S, Se) have been used. The thiirenium salts [tBu C SR] X (34) and [Ad C SR] X (35, 36) are prepared from the bis-tert-butylacetylene (2) and bis-adamantyl-acetylene (3) with R=Me SiCH CH and tBuMe SiCH CH . Attempts to cleave off the groups Me SiCH CH , tBuMe SiCH CH , and NCCH CH resulted in thiiranes 27, 30. No selenirane Ad Se (33) is formed from seleniranium salts, instead cleavage to the alkene (1) and diselenide (13, 15) occurs. The thiirenium salt [Ad C SCH CH SiMe ] Tf N (35) does not yield the thiirene Ad C S (37), the three-membered ring is cleaved, forming the alkyne (3) and disulfide (4). All compounds are characterized by ESI mass spectra, NMR spectra, and by quantum chemical calculations. Crystal structures of the salts 8, 12, 25, 17, 26, 36 and the thiiranes 27, 30 are presented.

Citing Articles

Attempts to Synthesize a Thiirane, Selenirane, and Thiirene by Dealkylation of Chalcogeniranium and Thiirenium Salts.

Poleschner H, Seppelt K Chemistry. 2020; 27(2):649-659.

PMID: 32737908 PMC: 7821244. DOI: 10.1002/chem.202003461.

References

Poleschner H, Seppelt K . First detection of a selenenyl fluoride ArSe-F by NMR spectroscopy: the nature of Ar2Se2/XeF2 and ArSe-SiMe3/XeF2 reagents. Chemistry. 2004; 10(24):6565-74. DOI: 10.1002/chem.200400596. View

Okamoto K, Nishibayashi Y, Uemura S, Toshimitsu A . Asymmetric carboselenenylation reaction of alkenes with aromatic compounds. Angew Chem Int Ed Engl. 2005; 44(23):3588-91. DOI: 10.1002/anie.200500573. View

Poleschner H, Seppelt K . Attempts to Synthesize a Thiirane, Selenirane, and Thiirene by Dealkylation of Chalcogeniranium and Thiirenium Salts. Chemistry. 2020; 27(2):649-659. PMC: 7821244. DOI: 10.1002/chem.202003461. View

Caton-Williams J, Huang Z . Synthesis and DNA-polymerase incorporation of colored 4-selenothymidine triphosphate for polymerase recognition and DNA visualization. Angew Chem Int Ed Engl. 2008; 47(9):1723-5. DOI: 10.1002/anie.200705213. View

Burdzinski G, Sliwa M, Zhang Y, Delbaere S . Early events in the photochemistry of 1,2,3-thiadiazole studied by ultrafast time-resolved UV-vis and IR spectroscopies. J Phys Chem A. 2011; 115(50):14300-5. DOI: 10.1021/jp2055238. View

Ono Y, Sugihara Y, Ishii A, Nakayama J . Synthesis and characterization of aliphatic alpha-dithiones, di(1-adamantyl)- and di-tert-butylethanedithiones. J Am Chem Soc. 2003; 125(40):12114-5. DOI: 10.1021/ja0371496. View

Poleschner H, Seppelt K . Seleniranium and Telluriranium Salts. Chemistry. 2018; 24(64):17155-17161. DOI: 10.1002/chem.201804307. View

Potapov V, Musalov M, Kurkutov E, Yakimov V, Khabibulina A, Musalova M . Remarkable Alkene-to-Alkene and Alkene-to-Alkyne Transfer Reactions of Selenium Dibromide and PhSeBr. Stereoselective Addition of Selenium Dihalides to Cycloalkenes. Molecules. 2020; 25(1). PMC: 6983007. DOI: 10.3390/molecules25010194. View

Tran T, Bricaud Q, Ocafrain M, Blanchard P, Roncali J, Lenfant S . Thiolate chemistry: a powerful and versatile synthetic tool for immobilization/functionalization of oligothiophenes on a gold surface. Chemistry. 2011; 17(20):5628-40. DOI: 10.1002/chem.201003687. View

10.

Denmark S, Collins W, Cullen M . Observation of direct sulfenium and selenenium group transfer from thiiranium and seleniranium ions to alkenes. J Am Chem Soc. 2009; 131(10):3490-2. DOI: 10.1021/ja900187y. View

11.

Brydon S, Ren Z, da Silva G, Lim S, Khairallah G, Rathjen M . Experimental and DFT Studies on the Identity Exchange Reactions between Phenyl Chalcogen Iranium Ions and Alkenes. J Phys Chem A. 2019; 123(38):8200-8207. DOI: 10.1021/acs.jpca.9b06004. View

12.

Bsaibess T, Guerro M, Le Gal Y, Sarraf D, Bellec N, Fourmigue M . Variable magnetic interactions between S = 1/2 cation radical salts of functionalizable electron-rich dithiolene and diselenolene Cp2Mo complexes. Inorg Chem. 2013; 52(4):2162-73. DOI: 10.1021/ic3025606. View

13.

Bock J, Daniliuc C, Bergander K, Muck-Lichtenfeld C, Hennecke U . Synthesis, structural characterisation, and synthetic application of stable seleniranium ions. Org Biomol Chem. 2019; 17(12):3181-3185. DOI: 10.1039/c9ob00078j. View

14.

Beckmann J, Hesse M, Poleschner H, Seppelt K . Formation of mixed-valent aryltellurenyl halides RX2TeTeR. Angew Chem Int Ed Engl. 2007; 46(43):8277-80. DOI: 10.1002/anie.200702341. View

15.

Poleschner H, Seppelt K . Selenirenium and tellurirenium ions. Angew Chem Int Ed Engl. 2008; 47(34):6461-4. DOI: 10.1002/anie.200801691. View

16.

Burdzinski G, Luk H, Reid C, Zhang Y, Hadad C, Platz M . The photochemistry of 4,5-carbomethoxy-1,2,3-thiadiazole: direct observation of thiirene formation and its decay in solution. J Phys Chem A. 2013; 117(22):4551-5. DOI: 10.1021/jp4003406. View

17.

Tani K, Murai T, Kato S . The first ammonium aromatic diselenoates: stable heavy congeners of aromatic carboxylic acid salts. J Am Chem Soc. 2002; 124(21):5960-1. DOI: 10.1021/ja026110i. View

18.

Poleschner H, Seppelt K . XeF(2) /fluoride acceptors as versatile one-electron oxidants. Angew Chem Int Ed Engl. 2013; 52(49):12838-42. DOI: 10.1002/anie.201307161. View

19.

Denmark S, Vogler T . Synthesis and reactivity of enantiomerically enriched thiiranium ions. Chemistry. 2009; 15(43):11737-45. DOI: 10.1002/chem.200901377. View

20.

Poleschner H, Ellrodt S, Malischewski M, Nakatsuji J, Rohner C, Seppelt K . Trip2C6H3SeF: the first isolated selenenyl fluoride. Angew Chem Int Ed Engl. 2011; 51(2):419-22. DOI: 10.1002/anie.201106708. View