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Issue 4, 2013
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Topological control in radical reactions of cholesterol in model dyads†

Dmytro Neshchadin,*a   Fabrizio Palumbo,b   M. Stefania Sinicropi,c   Inmaculada Andreu,d   Georg Gescheidta  and  Miguel A. Miranda*b  
Author affiliations

* Corresponding authors

a Institute of Physical and Theoretical Chemistry, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria
E-mail: neshchadin@tugraz.at
Fax: +43 316 87332202

b Instituto Universitario Mixto de Tecnología Química (UPV-CSIC), Universitat Politècnica de València, Avenida de los Naranjos s/n, 46022 Valencia, Spain
E-mail: mmiranda@qim.upv.es

c Dipartimento di Scienze Farmaceutiche, Università della Calabria, Arcavacata di Rende, 87036 Cosenza, Italy

d Unidad mixta de investigación IIS La Fe – UPV, Hospital La Fe, Avda. Campanar 21, 46009 Valencia, Spain

Abstract

Cholesterol is one of the most important building blocks of cell membranes. It is also one of the main targets for oxidation via Type I hydrogen abstraction (HA), which leads to a variety of physiological consequences in the human body. To provide a deeper understanding of the oxidation mechanism, steady-state 1H CIDNP, steady-state and laser-flash photolysis in combination with quantum mechanical calculations were applied to study HA in three model systems. The experiments involved photoinduced reactions in a cholesterol–benzophenone mixture and two derivatives, in which aminocholestene and benzophenone are covalently coupled yielding a dyad. It has been found, that a specific orientation of the benzophenone moiety toward the allylic hydrogens of cholesterol/aminocholestene is crucial for the efficient HA. Such a confined topology may play an important role for the particular oxidation of cholesterol in cell membranes.

Graphical abstract: Topological control in radical reactions of cholesterol in model dyads

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Article information

https://doi.org/10.1039/C3SC22109A
Submitted
29 Nov 2012
Accepted
22 Jan 2013
First published
23 Jan 2013
Chem. Sci., 2013,4, 1608-1614
Article type
Edge Article
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Topological control in radical reactions of cholesterol in model dyads

D. Neshchadin, F. Palumbo, M. S. Sinicropi, I. Andreu, G. Gescheidt and M. A. Miranda, Chem. Sci., 2013, 4, 1608
DOI: 10.1039/C3SC22109A

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