en
Scientific article
Open access
English

The Opening of 1,2-Dithiolanes and 1,2-Diselenolanes: Regioselectivity, Rearrangements, and Consequences for Poly(disulfide)s, Cellular Uptake and Pyruvate Dehydrogenase Complexes

Published inHelvetica Chimica Acta, vol. 102, no. 2, e1800209
Publication date2019
Abstract

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.

Research group
Citation (ISO format)
LAURENT, Quentin François Antoine, SAKAI, Naomi, MATILE, Stefan. The Opening of 1,2-Dithiolanes and 1,2-Diselenolanes: Regioselectivity, Rearrangements, and Consequences for Poly(disulfide)s, Cellular Uptake and Pyruvate Dehydrogenase Complexes. In: Helvetica Chimica Acta, 2019, vol. 102, n° 2, p. e1800209. doi: 10.1002/hlca.201800209
Main files (2)
Article (Published version)
accessLevelRestricted
Article (Accepted version)
accessLevelPublic
Identifiers
ISSN of the journal0018-019X
422views
228downloads

Technical informations

Creation02/19/2019 9:43:00 AM
First validation02/19/2019 9:43:00 AM
Update time03/15/2023 3:47:07 PM
Status update03/15/2023 3:47:06 PM
Last indexation01/17/2024 4:58:49 AM
All rights reserved by Archive ouverte UNIGE and the University of GenevaunigeBlack