102971-07-3Relevant academic research and scientific papers
Cycloadditions of adamantanethione S-methylide to heteromultiple bonds
Mloston, Grzegorz,Huisgen, Rolf,Polborn, Kurt
, p. 11475 - 11494 (1999)
Adamantanethione S-methylide (5) is an easily accessible thiocarbonyl S- ylide. Generated by N2 elimination from the cycloadduct of adamantanethione and diazomethane, the nucleophilic 1,3-dipole 5 reacts in situ with thiocarbonyl compounds furnishing 1,3-dithiolanes. 5 and carbon disulfide afford 1:1 and 2:1 cycloadducts. The structures are assessed by NMR spectra, a X-ray analysis, and C-S hydrogenolyses. The C=S group is an ambident electrophile; the ratios of regioisomeric adducts suggest that electronic effects favor the 4',5'-substituted 1,3-dithiolanes, whereas steric effects support the 2',4'-substituted systems. Electrophilic carbonyl compounds and 5 regiospecifically provide 2,4-disubstituted 1,3-oxathiolanes. Imines appear to be weak dipolarophiles vs. 5.
SCHOENBERG REACTIONS OF ADAMANTANETHIONE S-METHYLIDE
Mloston, Grzegorz,Huisgen, Rolf
, p. 2201 - 2206 (2007/10/02)
Nitrogen extrusion from 1,3,4-thiadiazoline-2-spiro-2'-adamantane at 40 deg C generates the thiocarbonyl ylide of the title which is intercepted in situ by dipolarophiles with CS double bond (aromatic and aliphatic thioketones, dithiocarboxylic esters, carbon disulfide, phenyl isothiocyanate).Both cycloaddition directions are used in the 1,3-dithiolane formation; the structural dependence and orientational forces are discussed.
