A novel oxime to pentathiepin cascade reaction

Macho, Sonia; Rees, Charles W.; Rodríguez, Teresa Rodríguez; Torroba, Tomás

doi:10.1039/b100366f

Cited by 25 publications

(17 citation statements)

References 18 publications

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“…Several synthetic benzopentathiepins are known 1 but heterocyclic fused systems are limited to isothiazolo, 7 pyrazolo, 8 1,3-dithiolo, 9 trithiolobenzo 10 and 1,2,3-dithiazolocyclopenta 11 derivatives. Methods for the synthesis of pentathiepins are very limited, the most common being treatment of the preformed o-dithiols and their precursors and salts with disulfur dichloride, S 2 Cl 2 , 7 S 3 Cl 2 12 or S 8 in liquid ammonia.…”

Section: Introductionmentioning

confidence: 99%

Direct synthesis of fused 1,2,3,4,5-pentathiepins

et al. 2005

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Treatment of nucleophilic heterocycles like pyrroles and thiophenes, and their tetrahydro derivatives, with S2Cl2 and DABCO in chloroform at room temperature provides a simple one-pot synthesis of fused mono and bispentathiepins. N-Methylpyrrole and its 2-chloro and 2,5-dichloro derivatives and N-methylpyrrolidine all give the same dichloropentathiepin 1a. N-Ethyl, isopropyl and tert-butylpyrrolidine behave similarly; the isopropylpyrrolidine also gives the bispentathiepin 6which undergoes an intriguing rearrangement to the symmetrical monopentathiepin 1c. N-Methyl and ethyl indole give either 2,3-dichloro derivatives 8 or the pentathiepinoindoles 9, depending upon the reaction conditions. Thiophene and tetrahydrothiophene give the pentathiepin 10. X-Ray crystal structures are provided for the pentathiepins 1a and 1d, and possible reaction pathways are suggested for the extensive cascade reactions reported.

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Section: Introductionmentioning

confidence: 99%

Direct synthesis of fused 1,2,3,4,5-pentathiepins

et al. 2005

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“…The best results were achieved by treating 1 with a three-fold excess of S 2 Cl 2 or a four-fold excess of pyridine in MeCN at 5 °C for 1 h which gave target 2 selectively in 81% yield (Scheme 1). The main feature of this and other S 2 Cl 2 /pyridine reactions is that the reaction mixtures are not tarry, and the product isolations do not require chromatography in contrast with the literature procedures [12,13,14,15].…”

Section: Resultsmentioning

confidence: 99%

“…Other synthetic precursors of fused 1,2,3-dithiazoles are cyclic oximes used in reactions with S 2 Cl 2 in the presence of organic bases such as N -ethyldiisopropylamine (Hünig’s base) and triisobutylamine. The disadvantage of this method is that no general procedure is established and in all cases arduous purification of products by column chromatography is required [12,13,14,15].…”

Section: Introductionmentioning

confidence: 99%

Fused 1,2,3-Dithiazoles: Convenient Synthesis, Structural Characterization, and Electrochemical Properties

et al. 2016

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Abstract:A new general protocol for synthesis of fused 1,2,3-dithiazoles by the reaction of cyclic oximes with S 2 Cl 2 and pyridine in acetonitrile has been developed. The target 1,2,3-dithiazoles fused with various carbocycles, such as indene, naphthalenone, cyclohexadienone, cyclopentadiene, and benzoannulene, were selectively obtained in low to high yields. In most cases, the hetero ring-closure was accompanied by chlorination of the carbocyclic moieties. With naphthalenone derivatives, a novel dithiazole rearrangement (15Ñ13) featuring unexpected movement of the dithiazole ring from α-to β-position, with respect to keto group, was discovered. Molecular structure of 4-chloro-5H-naphtho[1,2-d][1,2,3]dithiazol-5-one 13 was confirmed by single-crystal X-ray diffraction. Electrochemical properties of 13 were studied by cyclic voltammetry and a complex behavior was observed, most likely including hydrodechlorination at a low potential.

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“…117 Like the formation of other cyclopentadithiazoles, this reaction is accompanied by exhaustive chlorination (Scheme 85).…”

Section: Scheme 83mentioning

confidence: 99%