Torsten Linker

Why triple bonds protect acenes from oxidation and decomposition.

An experimental and computational study on the impact of functional groups on the oxidation stability of higher acenes is presented. We synthesized anthracenes, tetracenes, and pentacenes with various substituents at the periphery, identified their photooxygenation products, and measured the kinetics. Furthermore, the products obtained from thermolysis and the kinetics of the thermolysis are investigated. Density functional theory is applied in order to predict reaction energies, frontier molecular orbital interactions, and radical stabilization energies. The combined results allow us to describe the mechanisms of the oxidations and the subsequent thermolysis. We found that the alkynyl group not only enhances the oxidation stability of acenes but also protects the resulting endoperoxides from thermal decomposition. Additionally, such substituents increase the regioselectivity of the photooxygenation of tetracenes and pentacenes. For the first time, we oxidized alkynylpentacenes by using chemically generated singlet oxygen ((1)O(2)) without irradiation and identified a 6,13-endoperoxide as the sole regioisomer. The bimolecular rate constant of this oxidation amounts to only 1 × 10(5) s(-1) M(-1). This unexpectedly slow reaction is a result of a physical deactivation of (1)O(2). In contrast to unsubstituted or aryl-substituted acenes, photooxygenation of alkynyl-substituted acenes proceeds most likely by a concerted mechanism, while the thermolysis is well explained by the formation of radical intermediates. Our results should be important for the future design of oxidation stable acene-based semiconductors.

Remote substituent effects on the photooxygenation of 9,10-diarylanthracenes: strong evidence for polar intermediates

Two different reaction pathways in the photooxygenation of 9,10-diarylanthracenes are identified, with strong evidence for polar (forward, singlet oxygen addition) and radical (backward, thermolysis) intermediates.

9,10‐Diarylanthracenes as Molecular Switches: Syntheses, Properties, Isomerisations and Their Reactions with Singlet Oxygen

A series of 9,10-diarylanthracenes with various substituents at the ortho positions have been synthesised by palladium-catalysed cross-coupling reactions. Such compounds exhibit interesting physical properties and can be applied as molecular switches. Despite the high steric demand of the substituents, products were formed in moderate-to-good yields. In some cases, microwave conditions further improved yields. Bis-coupling afforded two isomers (syn and anti) that do not interconvert at room temperature. These products were easily separated and their relative stereochemistries were unequivocally assigned by NMR spectroscopy and X-ray analysis. The syn and anti isomers exhibit different physical properties (e.g., melting points and solubilities) and interconversion by rotation around the aryl-aryl axis commences at <100 degrees C for fluoro-substituted diarylanthracenes and at >300 degrees C for alkyl- or alkoxy-substituted diarylanthracenes. The reactions with singlet oxygen were studied separately and revealed different reactivities and reaction pathways. The yields and reactivities depend on the size and electronic nature of the substituents. The anti isomers form the same 9,10-endoperoxides as the syn species, occasionally accompanied by unexpected 1,4-endoperoxides as byproducts. Thermolysis of the endoperoxides exclusively yielded the syn isomers. The interesting rotation around the aryl-aryl axis allows the application of 9,10-diarylanthracenes as molecular switches, which are triggered by light and air under mild conditions. Finally, the oxygenation and thermolysis sequence provides a simple, synthetic access to a single stereoisomer (syn) from an unselective coupling step.

Biomimetic chain elongation of carbohydrates via radical carbon-carbon bond formation

Abstract Radical bond forming reactions can be used to mimic enzymatic aldol reactions between phosphoenol pyruvate and carbohydrates.

Selective reactions of transition-metal-generated radicals

Abstract In this microreview, we describe selective radical reactions in the presence of potassium permanganate, Mn(OAc)3, and cerium(IV) ammonium nitrate (CAN), which were developed in our group during the last years. The in situ generation of manganese(III) by potassium permanganate results in a low concentration of the oxidant, and allowed the chemoselective synthesis of H-atom transfer products in good yields. Furthermore, tandem reactions were developed to afford bicyclooctanes in diastereomerically pure form. Manganese(III) acetate was the reagent of choice for the selective synthesis of oxidation products. Ultrasonic irradiation remarkably accelerated such radical reactions and the method was applied for the simple and selective synthesis of tetra-acceptor-substituted alkenes from commercially available malonates. Due to the mild reaction conditions, CAN was superior to Mn(OAc)3 for applications in carbohydrate chemistry. Thus, 2-C-branched carbohydrates were synthesized from glycals in only one step and in excellent yields. The radical additions afford exclusively one regioisomer and exhibit a high degree of stereoselectivity. Finally, the anomeric radicals are trapped by CAN via a direct ligand transfer, which is important for the mechanistic understanding of transition-metal-mediated radical reactions.

Novel Anthracene Materials for Applications in Lithography and Reversible Photoswitching by Light and Air

Herein we demonstrate how the photoreaction between anthracenes and singlet oxygen ((1)O(2)) is employed for applications either as photoswitch or as photoresist. Thin films of the diaryl-alkyl anthracene 1 and the analogous oligomeric species 2 were irradiated under photomasks to generate pattern structures composed of 1/1-O(2) and 2/2-O(2). Kelvin probe force microscopy (KPFM) provided a powerful and nondestructive method to image the pattern information. The following studies based on AFM, KPFM and contact angle measurements unfold that the two species 1 and 2 underwent different progressions after the imaging step. Degrading is observed for the monomeric compound 1 and the pattern eventually becomes recognizable in topography. In the oxidized state (1-O(2)) the monomeric species remains physically stable. In consequence, the unreacted portion is removable and the remaining oxygenated form 1-O(2) is sufficiently stable to protect an underlying substrate (e.g., silver) from etching. Thus, the system 1/1-O(2) operates as photoresist. On the other hand, both states of the oligomer 2 remain stable. The film is stable up to temperatures >120 degrees C required to erase the pattern within acceptable time by cycloreversion. Anthracene 2 therefore acts as erasable and rewritable photochromic switch. The different behavior between 1 and 2 is explained by phase transitions which cause crystallization and finally ablation. Such transitions affect only the monomeric system 1/1-O(2) and not the oligomeric system 2/2-O(2). In conclusion, we designed two very similar materials based on diarylanthracenes, which can act either as a photoresist or as a rewritable photochromic switch.

Remarkable oxidation stability of glycals: Excellent substrates for cerium(IV)-mediated radical reactions

The remarkable stability of glycals under oxidative conditions becomes apparent by their redox data in solution, computed HOMO energies, and behavior on the addition of electrophilic radicals generated in the presence of cerium(IV) ammonium nitrate. Oxidation potentials up to 2.03 V vs ferrocene were obtained, which are exceptionally high for cyclic enol ethers but correlate nicely with the reaction times of the radical reactions. Protecting groups have a strong influence on the oxidation stability and HOMO energies of glycals as E(ox) is shifted from O-silyl over O-benzyl to O-acetyl by more than 500 mV. Interestingly, this effect must be transmitted through sigma-bonds, even up to the para-position of a benzoate group, as verified by a wide variation of remote substituents in the carbohydrate. Favorable interactions of the sigma*-orbital of the adjacent C-O bond with the HOMO of the double bond are proposed as a mechanistic rationale, which might be important for the redox behavior of other allylic systems. Finally, donors and acceptors in the 1-position exert the strongest influence on the oxidation stability, shifting the potentials by almost 1 V and resulting in different follow-up reactions of the cerium(IV)-mediated additions of malonates. It is the remarkable oxidation stability of glycals that makes them valuable building blocks in carbohydrate chemistry.

Intramolecular Transfer of Singlet Oxygen.

The intramolecular transfer of energy (FRET) and electrons (Dexter) are of great interest for the scientific community and are well-understood. In contrast, the intramolecular transfer of singlet oxygen ((1)O2), a reactive and short-lived oxygen species, has until now been unknown. This process would be very interesting because (1)O2 plays an important role in photodynamic therapy (PDT). Herein, we present the first successful intramolecular transfer of (1)O2 from a donor to acceptor. Also, we found a dependence of conformation and temperature comparable with those of FRET. We provide several pieces of evidence for the intramolecular character of this transfer, including competition experiments. Our studies should be interesting not only from the theoretical and mechanistic point of view but also for the design of new (1)O2 donors and applications in PDT.

Convenient Synthesis of Branched-Chain Glycosamines by Radical Addition of Nitromethane to Glycals

Radical addition-reduction-acetylation is the simple three-step sequence for the synthesis of branched-chain glycosamines 3 from glycals 1 and nitromethane (2). The intermediary formed 2-C-nitromethyl-pyranosides are valuable precursors for the synthesis of C-2 branched disaccharides.

Potassium permanganate-mediated radical reactions: chemoselective addition of acetone to olefins

Abstract A practical and efficient protocol for the radical addition of acetone (1) to olefins 2a-d, mediated by potassium permanganate, has been developed. The in situ generation of manganese(III) allows the chemoselective synthesis of saturated C-C bond formation products 4a-d in 39–58% yield. Furthermore, the required amount of manganese is reduced drastically in account of the catalytic reaction cycle.