Arbeitskreis Lindel

Marine Naturstoffe - Bausteine des Lebens

Have you thought about organic synthesis lately?

Aktuelles Gruppenbild vom Arbeitskreis Lindel

Aktuelle Publikationen:

J.-N. Schäckermann, T. Lindel, "Synthesis and Photooxidation of the Trisubstituted Oxazole Fragment of the Marine Natural Product Salarin C", Org. Lett. 2017, 19, 2306-2309.

The eastern section of the macrocyclic marine natural product salarin C from the sponge Fascaplysinopsis sp. was synthesized employing a halogen dance reaction to assemble the trisubstituted oxazole moiety. The synthesis was inspired by Kashman’s hypothesis on the biomimetic oxidation of salarin C to salarin A. Clean conversion to the triacylamine partial structure of salarin A occurred on treatment with photochemically generated singlet oxygen. Thus, a Wasserman-type oxidative rearrangement is chemically possible in this case.

N. E. Kanitz, T. Lindel, Photoreactivity of monofluorinated 2-azidobenzimidazoles towards carboxylic acids A", Z. Naturforsch. 2016, 71b, 1287–1300.

Aiming at the development of new photolabeling agents, the synthesis and photoreactivity of all monofluorinated derivatives of 2-azido-1-methylbenzimidazole are described. In the case of 4-, 5-, or 7-fluorination, irradiation in the presence of carboxylic acids (300 nm, Rayonet) afforded the monofluorinated 2-amino-6-acyloxybenzimidazoles in a regioselective manner, presumably after conversion of the initially formed nitrene to the N-cyanodiazaxylylene. Incorporation of chloride was also possible, and yields were comparable to those observed for the non-fluorinated parent compound. When blocking the reactive 6-position by a fluoro substituent, the title reaction was not possible. The analysis of the 19F NMR chemical shifts of the 5- and 7-monofluorinated products allowed the distinction between carboxylates and other nucleophiles.

N. Marsch, M. Kock, T. Lindel, Study on the synthesis of the cyclopenta[f]indole core of raputindole A", Beilstein J. Org. Chem. 2016, 12, 334–342.

The raputindoles from the rutaceous tree Raputia simulans share a cyclopenta[f]indole partial structure the synthesis of which is subject of this investigation. An efficient route to a series of 1,5-di(indol-6-yl)pentenones was developed via Mo/Au-catalyzed Meyer–Schuster rearrangement of tertiary propargylic alcohol precursors. However, none of the enones underwent the desired Nazarov cyclization to a cyclopenta[f]indole. More suitable were 6-hydroxyallylated indolines which gave good yields of cyclopenta[f]indolines after treatment with SnCl4, as soon as sterically demanding β-cyclocitral adducts were reacted. Most successful were Pt(II) and Au(I)-catalyzed cyclizations of N-TIPS-protected indolin-6-yl-substituted propargylacetates which provided the hydrogenated tricyclic cyclopenta[f]indole core system in high yield.