Premium
Reactions of Thiobenzophenone S ‐Methylide with Thiocarbonyl Compounds
Author(s) -
Huisgen Rolf,
Li Xingya,
Mloston Grzegorz,
Fulka Claudia
Publication year - 2000
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(200005)2000:9<1695::aid-ejoc1695>3.0.co;2-4
Subject(s) - chemistry , ketene , isomerization , methylene , dithiolane , ring (chemistry) , medicinal chemistry , photochemistry , stereochemistry , organic chemistry , catalysis
2,5‐Dihydro‐2,2‐diphenyl‐1,3,4‐thiadiazole ( 4 ) eliminates N 2 at −45 °C and generates thiobenzophenone S ‐methylide ( 5 ), which is intercepted by dipolarophiles. The 1,3‐cycloadditions of 5 with thiones (aromatic and aliphatic thioketones, dithioesters, trithiocarbonate) furnish 1,3‐dithiolanes 7 , in which the substituents, even voluminous ones, appear in the proximal 4‐ and 5‐positions. The reaction of 5 with adamantanethione furnishes 7h and 4,4,5,5‐tetraphenyl‐1,3‐dithiolane ( 7a ) in a ratio of 4:1; a methylene transfer is involved, and the mechanistic pathways are discussed. The cycloadduct 7f originating from 5 and diphenyl trithiocarbonate undergoes an isomerization which consists of ionization and ring‐opening leading to a ketene dithioacetal structure.