(-)-Thallusin, isolated from a marine bacterium, is the only known natural product to act as an algal morphogenesis inducer. Because (-)-thallusin can only be obtained in exceedingly limited amounts from microbial cultivation, a synthetic supply of this compound is highly desirable. Here, we describe a novel synthetic pathway to (±)-thallusin and the first asymmetric synthesis of (-)-thallusin utilizing the enzymatic hydrolysis resolution with the combination of lipase PS-30 and lipase M Amamo-10.
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http://dx.doi.org/10.1021/jo501720b | DOI Listing |
Chemistry
March 2024
Friedrich Schiller University Jena, Institute of Organic Chemistry and Macromolecular Chemistry, Humboldtstr. 10, D-07743, Jena, Germany.
A fully enantioselective, catalytic synthesis of the algal morphogen (-)-thallusin using polyene cyclization chemistry is reported. The synthesis features dedicated precursor design, introduction of a TMS-substituted arene as a regioselective terminator, very high enantiomer excess (ee) on gram scale, and productive scaffold functionalization. Furthermore, an ee determination methodology of thallusin samples was developed, and the ee of biosynthesized thallusin was determined.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2022
Friedrich-Schiller-Universität Jena, Institut für Organische Chemie und Makromolekulare Chemie, Humboldtstr. 10, 07743, Jena, Germany.
Chemical mediators are key compounds for controlling symbiotic interactions in the environment. Here, we disclose a fully stereoselective total synthesis of the algae differentiation factor (-)-thallusin that utilizes sophisticated 6-endo-cyclization chemistry and effective late-stage sp -sp -couplings using non-toxic reagents. An EC of 4.
View Article and Find Full Text PDFSemin Cell Dev Biol
January 2023
Institute for Inorganic and Analytical Chemistry, Jena School for Microbial Communication, Friedrich Schiller University Jena, Lessingstraße 8, 07743 Jena, Germany. Electronic address:
The marine green macroalga Ulva (Chlorophyta, Ulvales), also known as sea lettuce, coexists with a diverse microbiome. Many Ulva species proliferate in nature and form green algal blooms ("green tides"), which can occur when nutrient-rich wastewater from agricultural or densely populated areas is flushed into the sea. Bacteria are necessary for the adhesion of Ulva to its substrate, its growth, and the development of its blade morphology.
View Article and Find Full Text PDFJ Org Chem
September 2014
Faculty of Pharmaceutical Science, Tokushima Bunri University, Yamashiro-cho, Tokushima 770-8514, Japan.
(-)-Thallusin, isolated from a marine bacterium, is the only known natural product to act as an algal morphogenesis inducer. Because (-)-thallusin can only be obtained in exceedingly limited amounts from microbial cultivation, a synthetic supply of this compound is highly desirable. Here, we describe a novel synthetic pathway to (±)-thallusin and the first asymmetric synthesis of (-)-thallusin utilizing the enzymatic hydrolysis resolution with the combination of lipase PS-30 and lipase M Amamo-10.
View Article and Find Full Text PDFOrg Lett
May 2006
Department of Chemistry, Brandeis University, Waltham, Massachusetts 02454-9110, USA.
[reaction: see text] A three-step route from sclareol oxide (6) to bromo ester 4 in 53% overall yield was achieved using the efficient oxidation of an allylic bromide to an enal with bis(2,4,6-trimethylpyridine)silver(I) hexafluorophosphate in DMSO. Stille coupling of bromo ester 4 with stannylpyridine 5 gave the trimethyl ester of ent-thallusin in 54-92% yield by the stoichiometric conversion of 4 to a vinyl palladium intermediate prior to the addition of 5 to the reaction.
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