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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents



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ID: 708199.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Mechanical Manipulation of Chemical Reactions: Reactivity Switching of Bergman Cyclizations.
Authors:Krupicka, Martin; Sander, Wofram; Marx, Dominik
Language:English
Date of Publication (YYYY-MM-DD):2014
Title of Journal:Journal of Physical Chemistry Letters
Journal Abbrev.:J.Phys.Chem.Lett.
Volume:5
Issue / Number:5
Start Page:905
End Page:909
Review Status:Peer-review
Audience:Experts Only
Abstract / Description:Photoswitches incorporated into molecular frameworks have been used since a long time to trigger chemical processes on demand. Here, it is shown how mechanophores can be used as switches in order to drastically change the reactivity of a neighboring functional group as a function of external stress. The reactivities of cyclic enediynes, which are highly toxic agents when undergoing Bergman cyclization, roughly correlate with the distance between the bond-forming carbons in many cases. It is demonstrated how this distance, and thus enediyne reactivity, can be tuned upon applying mechanical stress. Depending on suitable substitution patterns, chemically inert species can be turned into highly reactive ones and vice versa, thus extending the concept of photoswitching to mechanoswitching. Moreover, depending on the derivative, it is found that C-1-C-5 cyclization becomes energetically preferred over the Bergman (C-1-C-6) pathway at nano-Newton forces, thus leading to a force-induced switch in
External Publication Status:published
Document Type:Article
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
Identifiers:ISI:000332755700026 [ID No:1]
ISSN:1948-7185 [ID No:2]
DOI:10.1021/jz402644e [ID No:3]
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