ChemInform Abstract: Spectral and Chemical Properties of Dimethyldioxirane as Determined by Experiment and ab Initio Calculations.

Adam, Waldemar; Chan, Yuk Yee; Cremer, Dieter; Gauß, Jürgen; Scheutzow, Dieter; Schindler, Michael

doi:10.1002/chin.198801191

Cited by 2 publications

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“…a-Methylation of the thiolactone 13, to 14, followed by a-oxygenation using a modified Vedejs the same dioxodithiolane residue in naturally derived leinamycin. * In a modification of this general approach, we found that the 1,2-dithiolane intermediate 8 could also be synthesised from the 0-thiolactone 13 following conversion into 16 (using H,S-Et,N, then FeCl,) and a-methylation/a-oxidation, as before. In a second and perhaps more direct approach to the 1,2dithiolane 8 we found that, when the sodium glycidate 17, derived in two steps from acetone and ethyl a-chloropropanoate, was stirred with sodium sulfide in methanolI4 at room * The full stereochemical detail of leinamycin has not been published.…”

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confidence: 84%

Synthetic approaches towards the novel 1,3-dioxo-1,2-dithiolane moiety in the antitumour antibiotic substance leinamycin

Pattenden¹,

Shuker²

1992

J. Chem. Soc., Perkin Trans. 1

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A number of complementary synthetic approaches t o the P-thiolactone intermediate 9 for elaboration to the novel 1,3-dioxo-1,2-dithiolane moiety 6 found in the antitumour antibiotic substance leinamycin 1 are described.Thus, deprotection of the benzylthio ether produced from 3-methylbut-2-enoic acid and toluenea-thiol, leads to the mercapto acid 12 which on cyclisation produces the thiolactone 13. a-Methylation of the thiolactone 13, followed by a-oxygenation then gives rise t o the substituted f3-thiolactone 9. The P-thiolactone 9 is also produced when: (i) the sodium glycidate 17 is stirred with sodium sulfide leading to 18, followed by thiolactonisation; (ii) thioacetone is treated with the ketene derived from 2-acetoxypropanoyl chloride; and (iii) by irradiation of 3-methyl-2-trimethylsilyloxybut-2-ene 22 with thiophosgene leading to 23, followed by hydrolysis.

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