@article{FudickarBauchIhmelsetal.2021,
  author    = {Fudickar, Werner and Bauch, Marcel and Ihmels, Heiko and Linker, Torsten},
  title     = {DNA-triggered enhancement of singlet oxygen production by pyridinium alkynylanthracenes},
  series = {Chemistry - a European journal},
  volume    = {27},
  journal   = {Chemistry - a European journal},
  number    = {54},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1521-3765},
  doi       = {10.1002/chem.202101918},
  pages     = {13591 -- 13604},
  year      = {2021},
  abstract  = {There is an ongoing interest in O-1(2) sensitizers, whose activity is selectively controlled by their interaction with DNA. To this end, we synthesized three isomeric pyridinium alkynylanthracenes 2 o-p and a water-soluble trapping reagent for O-1(2). In water and in the absence of DNA, these dyes show a poor efficiency to sensitize the photooxygenation of the trapping reagent as they decompose due to electron transfer processes. In contrast, in the presence of DNA O-1(2) is generated from the excited DNA-bound ligand. The interactions of 2 o-p with DNA were investigated by thermal DNA melting studies, UV/vis and fluorescence spectroscopy, and linear and circular dichroism spectroscopy. Our studies revealed an intercalative binding with an orientation of the long pyridyl-alkynyl axis parallel to the main axis of the DNA base pairs. In the presence of poly(dA : dT), all three isomers show an enhanced formation of singlet oxygen, as indicated by the reaction of the latter with the trapping reagent. With green light irradiation of isomer 2 o in poly(dA : dT), the conversion rate of the trapping reagent is enhanced by a factor >10. The formation of O-1(2) was confirmed by control experiments under anaerobic conditions, in deuterated solvents, or by addition of O-1(2) quenchers. When bound to poly(dG : dC), the opposite effect was observed only for isomers 2 o and 2 m, namely the trapping reagent reacted significantly slower. Overall, we showed that pyridinium alkynylanthracenes are very useful intercalators, that exhibit an enhanced photochemical O-1(2) generation in the DNA-bound state.},
  language  = {en}
}
@article{BauchFudickarLinker2021,
  author    = {Bauch, Marcel and Fudickar, Werner and Linker, Torsten},
  title     = {Stereoselective [4+2] Cycloaddition of Singlet Oxygen to Naphthalenes Controlled by Carbohydrates},
  series = {Molecules : a journal of synthetic chemistry and natural product chemistry},
  volume    = {16},
  journal   = {Molecules : a journal of synthetic chemistry and natural product chemistry},
  number    = {4},
  publisher = {MDPI},
  address   = {Basel},
  issn      = {1420-3049},
  doi       = {10.3390/molecules26040804},
  pages     = {17},
  year      = {2021},
  abstract  = {Stereoselective reactions of singlet oxygen are of current interest. Since enantioselective photooxygenations have not been realized efficiently, auxiliary control is an attractive alternative. However, the obtained peroxides are often too labile for isolation or further transformations into enantiomerically pure products. Herein, we describe the oxidation of naphthalenes by singlet oxygen, where the face selectivity is controlled by carbohydrates for the first time. The synthesis of the precursors is easily achieved starting from naphthoquinone and a protected glucose derivative in only two steps. Photooxygenations proceed smoothly at low temperature, and we detected the corresponding endoperoxides as sole products by NMR. They are labile and can thermally react back to the parent naphthalenes and singlet oxygen. However, we could isolate and characterize two enantiomerically pure peroxides, which are sufficiently stable at room temperature. An interesting influence of substituents on the stereoselectivities of the photooxygenations has been found, ranging from 51:49 to up to 91:9 dr (diastereomeric ratio). We explain this by a hindered rotation of the carbohydrate substituents, substantiated by a combination of NOESY measurements and theoretical calculations. Finally, we could transfer the chiral information from a pure endoperoxide to an epoxide, which was isolated after cleavage of the sugar chiral auxiliary in enantiomerically pure form.},
  language  = {en}
}
@misc{BauchFudickarLinker2021,
  author    = {Bauch, Marcel and Fudickar, Werner and Linker, Torsten},
  title     = {Stereoselective [4+2] Cycloaddition of Singlet Oxygen to Naphthalenes Controlled by Carbohydrates},
  series = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  journal   = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  number    = {1116},
  issn      = {1866-8372},
  doi       = {10.25932/publishup-49336},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-493361},
  pages     = {19},
  year      = {2021},
  abstract  = {Stereoselective reactions of singlet oxygen are of current interest. Since enantioselective photooxygenations have not been realized efficiently, auxiliary control is an attractive alternative. However, the obtained peroxides are often too labile for isolation or further transformations into enantiomerically pure products. Herein, we describe the oxidation of naphthalenes by singlet oxygen, where the face selectivity is controlled by carbohydrates for the first time. The synthesis of the precursors is easily achieved starting from naphthoquinone and a protected glucose derivative in only two steps. Photooxygenations proceed smoothly at low temperature, and we detected the corresponding endoperoxides as sole products by NMR. They are labile and can thermally react back to the parent naphthalenes and singlet oxygen. However, we could isolate and characterize two enantiomerically pure peroxides, which are sufficiently stable at room temperature. An interesting influence of substituents on the stereoselectivities of the photooxygenations has been found, ranging from 51:49 to up to 91:9 dr (diastereomeric ratio). We explain this by a hindered rotation of the carbohydrate substituents, substantiated by a combination of NOESY measurements and theoretical calculations. Finally, we could transfer the chiral information from a pure endoperoxide to an epoxide, which was isolated after cleavage of the sugar chiral auxiliary in enantiomerically pure form.},
  language  = {en}
}
@article{BauchKlaperLinker2017,
  author    = {Bauch, Marcel and Klaper, Matthias and Linker, Torsten},
  title     = {Intermediates in the cleavage of endoperoxides},
  series = {Journal of physical organic chemistry},
  volume    = {30},
  journal   = {Journal of physical organic chemistry},
  publisher = {Wiley},
  address   = {Hoboken},
  issn      = {0894-3230},
  doi       = {10.1002/poc.3607},
  pages     = {6},
  year      = {2017},
  abstract  = {The decomposition of anthracene endoperoxides has been investigated under various conditions. Thermolyses proceed via radical intermediates and afford anthracenes and rearrangement products, depending on the substitution pattern. Interestingly, not only the O-O but also the C-O bond can be cleaved homolytically. Under basic conditions fragmentations take place, affording anthraquinone, and reactive oxygen species. This mechanism explains the often observed decomposition of endoperoxides during work-up. Finally, an acid-catalyzed cleavage has been observed under release of hydrogen peroxide. The results should be interesting for the mechanistic understanding of peroxide decomposition and the endoperoxides might serve as mild sources of reactive oxygen species for future applications. Copyright (C) 2016 John Wiley \& Sons, Ltd.},
  language  = {en}
}
@article{BauchKrtitschkaLinker2017,
  author    = {Bauch, Marcel and Krtitschka, Angela and Linker, Torsten},
  title     = {Photooxygenation of oxygen-substituted naphthalenes},
  series = {Journal of physical organic chemistry},
  volume    = {30},
  journal   = {Journal of physical organic chemistry},
  publisher = {Wiley},
  address   = {Hoboken},
  issn      = {0894-3230},
  doi       = {10.1002/poc.3734},
  pages     = {6803 -- 6813},
  year      = {2017},
  abstract  = {The reaction of oxygen-substituted naphthalenes with singlet oxygen (O-1(2)) has been investigated, and labile endoperoxides have been isolated and characterized at -78 degrees C for the first time. Low-temperature kinetics by UV spectroscopy revealed that alkoxy and silyloxy substituents remarkably increase the rate of photooxygenations compared to 1,4-dimethylnaphthalene, whereas acyloxy-substituted acenes are inert towards O-1(2). The reactivities nicely correlate with HOMO energies and free activation energies, which we determined by density functional theory calculations. The lability of the isolated endoperoxides is due to their very fast back reaction to the corresponding naphthalenes even at -20 degrees C under release of O-1(2), making them to superior sources of this reactive species under very mild conditions. Finally, a carbohydrate-substituted naphthalene has been synthesized, which reacts reversibly with O-1(2) and might be applied for enantioselective oxidations in future work.},
  language  = {en}
}
@article{BauchBoettcherBornscheueretal.2016,
  author    = {Bauch, Marcel and B{\"o}ttcher, Dominique and Bornscheuer, Uwe T. and Linker, Torsten},
  title     = {Enzymatic Cleavage of Aryl Acetates},
  series = {ChemCatChem : heterogeneous \& homogeneous \& bio- \& nano-catalysis ; a journal of ChemPubSoc Europe},
  volume    = {8},
  journal   = {ChemCatChem : heterogeneous \& homogeneous \& bio- \& nano-catalysis ; a journal of ChemPubSoc Europe},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  organization    = {HESS Collaboration},
  issn      = {1867-3880},
  doi       = {10.1002/cctc.201600678},
  pages     = {2853 -- 2857},
  year      = {2016},
  abstract  = {Seven enzymes have been screened for the cleavage of aryl acetates. Phenyl and naphthyl acetates react with lipases and esterases, whereas the sterically demanding anthracene acetate gave a conversion only with porcine liver esterase and esterase 2 from Bacillus subtilis (BS2). These two enzymes have been employed on a preparative (0.5 mmol) scale and afforded cleavage products in 91 and 94\% yields, even for anthracene acetate. Thus, this method is superior to chemical cleavage with catalytic amounts of sodium methoxide (Zemplen conditions), which gave only low conversions. Finally, regioselectivity has been achieved with an anthracene bisacetate, in which an ethyl group controls the cleavage of the first acetate. This indicates that steric interactions play a crucial role in the enzymatic cleavage of aryl acetates, which might be interesting for future applications or the development of enzyme inhibitors.},
  language  = {en}
}