期刊
HELVETICA CHIMICA ACTA
卷 102, 期 2, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/hlca.201800209
关键词
diselenides; disulfides; ring tension; regioselectivity; migration; rearrangement; constitutional isomers; reactive intermediates
资金
- University of Geneva
- Swiss National Centre of Competence in Research (NCCR) Chemical Biology
- NCCR Molecular Systems Engineering
- Swiss NSF
The thiol-mediated opening of 3-alkyl-1,2-dithiolanes and diselenolanes is described. The thiolate nucleophile is shown to react specifically with the secondary chalcogen atom, against steric demand, probably because the primary chalcogen atom provides a better leaving group. Once released, this primary chalcogen atom reacts with the obtained secondary dichalcogenide to produce the constitutional isomer. Thiolate migration to the primary dichalcogenide equilibrates within ca. 20 ms at room temperature at a 3 : 2 ratio in favor of the secondary dichalcogenide. The clarification of this focused question is important for the understanding of multifunctional poly(disulfide)s obtained by ring opening disulfide exchange polymerization of 3-alkyl-1,2-dithiolanes, to rationalize the cellular uptake mediated by 3-alkyl-1,2-diselenolanes as molecular walkers and, perhaps, also of the mode of action of pyruvate dehydrogenase complexes. The isolation of ring-opened diselenolanes is particularly intriguing because dominant selenophilicity disfavors ring opening strongly.
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