Adamantanethione

Reactions of polycyclic thioketones with a phosphonylated carbanion

“…In the same paper, the reaction of 1a with vinylmagnesium bromide is reported to yield the product of the carbophilic addition exclusively (cf. [6]). The reaction with 1-methoxyallenyllithium occurs in the carbophilic mode and leads to the corresponding 2-allenyladamantane-2-thiolate, which after quenching with water yields thiirane 5 as a product of an intramolecular nucleophilic addition (Scheme 2).…”

“…Phosphonylated carbanions are widely applied in reactions with carbonyl compounds [8], but no reactions with thiocarbonyl derivatives have been reported to date. In the present paper, the first results of the reactions of the carbanion generated from dimethyl methylphosphonate with the polycyclic thioketone 1a (adamantanethione) and the recently prepared 'cage' thioketone 1b (pentacyclo[5.4.0.0 2,6 .0 3,10 .0 5,9 ]undecane-8-thione) [9] are described.…”

Reactions of (1,3,3-Trichloro-2,2,4,4-tetramethylcyclobutyl)sulfenyl Chloride with Some S- and O-Nucleophiles

“…In general, thioketones are rather unstable compounds, 1 and there is a limited number of aliphatic and cycloaliphatic representatives, which can be handled without special precautious. It is well documented that sterically crowded and non-enolizable thioketones are relatively stable, and for this reason, adamantanethione (1) 2 as well as 2,2,4,4-tetramethylcyclobutanethiones 2a,b 3,4 are models of choice for studies on the reactivity of the C=S group. In the last two decades, thioketones 1 and 2a,b were extensively explored as dipolarophiles and as precursors of so called 'sulfur-centered 1,3-dipoles' such as thiocarbonyl ylides, 5 S-sulfides, 6 S-imides, 7 and S-oxides.…”

“…We propose that the nucleophilic substitution leads to the propargyl sulfenate 10, which spontaneously undergoes a [2,3]-sigmatropic rearrangement to give 11. This type of rearrangement was previously reported for reactions of propargyl alcohol with variably substituted halomethyl sulfenyl chlorides (e.g.…”

“…2:1). The formation of 13 results from a [2,3]-sigmatropic rearrangement of the initially formed allyl sulfenate 12. The precursor of the unexpected 14 is either 12 or 13, which, by elimination of allyl chloride, can be transformed into the sulfine 14.…”