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Attempts to Synthesize a Thiirane, Selenirane, and Thiirene by Dealkylation of Chalcogeniranium and Thiirenium Salts
Author(s) -
Poleschner Helmut,
Seppelt Konrad
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202003461
Subject(s) - diselenide , thiirane , chemistry , alkene , medicinal chemistry , alkylation , mass spectrum , stereochemistry , crystal structure , nmr spectra database , alkyne , cleavage (geology) , acetylene , salt (chemistry) , crystallography , ring (chemistry) , spectral line , organic chemistry , selenium , catalysis , ion , materials science , physics , astronomy , fracture (geology) , composite material
Thiiranium salts [Ad 2 SR] + X − ( 5 , 8 , 9 , 11 , 12 ; X − =Tf 2 N − (Tf=CF 3 SO 2 ), SbCl 6 − ) and seleniranium salts [Ad 2 SeR] + X − ( 14 , 16 , 17 , 23 – 25 ; X − =Tf 2 N − , BF 4 − , CHB 11 Cl 11 − , SbCl 6 − ) are synthesized from strained alkene bis(adamantylidene) ( 1 ). The disulfides and the diselenides (Me 3 SiCH 2 CH 2 E) 2 ( 4 , 13 ), ( t BuMe 2 SiCH 2 CH 2 E) 2 ( 7 , 22 ), and (NCCH 2 CH 2 E) 2 ( 10 , 15 ; E=S, Se) have been used. The thiirenium salts [ t Bu 2 C 2 SR] + X − ( 34 ) and [Ad 2 C 2 SR] + X − ( 35 , 36 ) are prepared from the bis‐ tert ‐butylacetylene ( 2 ) and bis‐adamantyl‐acetylene ( 3 ) with R=Me 3 SiCH 2 CH 2 and t BuMe 2 SiCH 2 CH 2 . Attempts to cleave off the groups Me 3 SiCH 2 CH 2 , t BuMe 2 SiCH 2 CH 2 , and NCCH 2 CH 2 resulted in thiiranes 27 , 30 . No selenirane Ad 2 Se ( 33 ) is formed from seleniranium salts, instead cleavage to the alkene ( 1 ) and diselenide ( 13 , 15 ) occurs. The thiirenium salt [Ad 2 C 2 SCH 2 CH 2 SiMe 3 ] + Tf 2 N − ( 35 ) does not yield the thiirene Ad 2 C 2 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.