Cycloadditions of adamantanethione S-methylide to heteromultiple bonds

Citation
G. Mloston et al., Cycloadditions of adamantanethione S-methylide to heteromultiple bonds, TETRAHEDRON, 55(38), 1999, pp. 11475-11494
Citations number
45
Categorie Soggetti
Chemistry & Analysis","Organic Chemistry/Polymer Science
Journal title
TETRAHEDRON
ISSN journal
00404020 → ACNP
Volume
55
Issue
38
Year of publication
1999
Pages
11475 - 11494
Database
ISI
SICI code
0040-4020(19990917)55:38<11475:COASTH>2.0.ZU;2-L
Abstract
Adamantanethione S-methylide (5) is an easily accessible thiocarbonyl S-yli de. Generated by N-2 elimination from the cycloadduct of adamantanethione a nd diazomethane, the nucleophilic 1,3-dipole 5 reacts in situ with thiocarb onyl 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 electrophil e; the ratios of regioisomeric adducts suggest that electronic effects favo r the 4',5'-substituted 1,3-dithiolanes, whereas steric effects support the 2',4'-substituted systems. Electrophilic carbonyl compounds and 5 regiospe cifically provide 2,4-disubstituted 1,3-oxathiolanes. Imines appear to be w eak dipolarophiles vs. 5. (C) 1999 Elsevier Science Ltd. All rights reserve d.