Reactions of Chlorosulfanyl Derivatives of Cyclobutanones with Different Nucleophiles

Abstract

The reactions of 3-chloro-3-(chlorosulfanyl)-2,2,4,4-tetramethylcyclobutan-1-one (2) with N, O, S, and P nucleophiles occur by substitution of Cl at the S-atom. Whereas, in the cases of secondary amines, alkanols, phenols, thiols, thiophenols, and di-and trialkyl phosphates, the initially formed substitution products were obtained, the corresponding products with allyl and propargyl alcohols undergo a [2,3]-sigmatropic rearrangement to give allyl and allenyl sulfoxides, respectively. Analogous substitution reactions were observed when 3-chloro-3-(chlorodisulfanyl)-2,2,4,4-tetramethylcyclobutan-1-one (3) was treated with N, O, and S nucleophiles. The reaction of 3 with Et 3 A C H T U N G T R E N N U N G P led to an unexpected product via cleavage of the SÀS bond (cf. Scheme 13). In the reactions of 2 with primary amines and H 2 O, the substitution products react further via elimination of HCl to yield the corresponding thiocarbonyl S-imides and the thiocarbonyl S-oxide, respectively. Whereas the latter could be isolated, the former were not stable but could be intercepted by MeOH (Scheme 4) or adamantanethione (Scheme 5). The structures of some of the substitution products were established by X-ray crystallography.

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

“…* In a second experiment, in the absence of Et 3 N, the disulfane 7 was formed in small amount, and 6 could be isolated by crystallization of the mixture from petroleum ether. This result confirms that 3c, in analogy to earlier published reactions with 3a,b, 10,11 easily undergoes substitution with S-nucleophiles at the S-atom. Under analogous reaction conditions, in the presence of Et 3 N, the colored organic solution of thiocamphor (5) turned colorless after 10 min.…”

“…(Propa-1,2-dienyl) (1,3,3-trichloro-2,2,4,4-tetramethylcyclobutyl)sulfoxide (11) Stirring was continued for 1 h at room temperature and the solvent was evaporated. The residue was washed with diethyl ether (for the purpose to remove inorganic salts) and product 13 was separated from the sulfine 14 9 (isolated as the less polar fraction, 53 mg (23%)) using preparative layer chromatography and CH 2 Cl 2 /petroleum ether 1:1 as the eluent.…”

Amination of N-(Organodithio)phthalimides for the Modular Synthesis of Aminodisulfides

“…Although the preparation of symmetrical diaminodisulfides via the reaction of S 2 Cl 2 with amine is well established (Figure a), the sequential introduction of carbon and amine nucleophiles or two distinct amine nucleophiles into S 2 Cl 2 is problematic due to the lack of chemoselectivity between the first and second nucleophilic displacement events. As such, only a few specific unsymmetrical aminodisulfides have been synthesized by this approach (Figure b). , Recently, Jiang et al developed monoalkoxy and dialkoxy disulfide reagents that enable the introduction of amino substituents via S–O bond cleavage (Figure c) . While the monoalkoxy reagents can be readily aminated with various amines, each reagent requires a multistep preparation (Figure c-1) .…”

Addition Reactions of Sulfenyl and Sulfinyl Chlorides with 3‐Phenyl‐1‐azabicyclo[1.1.0]butane

“…Sulfinyl and sulfenyl chlorides are known to react with N-nucleophiles to yield sulfinamides and sulfenamides (sulfanyl-amines), respectively [11a,b] [14]. They are formed via a substitution reaction in which HCl is eliminated.…”