97462-26-5

Upstream product

• 100-52-7 benzaldehyde 
• 31934-33-5 1,3,4-thiadiazoline-2-spiro-2'-adamantane 
• 23695-65-0 adamantane-2-thione 
• 31934-33-5 2',5'-dihydrospiro[adamantane-2,2'-(1,3,4)-thiadiazole] 

Relevant academic research and scientific papers

Cycloadditions of adamantanethione S-methylide to heteromultiple bonds

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.

ADAMANTANETHIONE AND DIAZOMETHANE; A RE-EXAMINATION

The title reaction affords the two regioisomeric cycloadducts which were isolated and differ in their rates of nitrogen extrusion; the spiro-1,3,4-thiadiazoline furnishes the adamantanethione S-methylide which undergoes in situ cycloadditions to electron-deficient dipolarophiles.

RECENT DEVELOPMENTS OF THE CHEMISTRY OF THIOCARBONYL YLIDES

The cycloaddition of diazoalkanes to CS double bonds furnishes 1,3,4-thiadiazolines which give rise to thiocarbonyl ylides and N2 in cycloreversion.Thiocarbonyl ylides are nucleophilic 1,3-dipoles which are interceptible by thiones or electron-deficient alkenes and alkynes as dipolarophiles affording 1,3-dithiolanes, dihydrothiophenes and thiolanes, respectively.In the absence of reaction partners, thiocarbonyl ylides undergo electrocyclization, dimerization, β-H abstraction or Wagner-Meerwein rearrangement.