A short, nine-step, highly enantioselective synthesis of (-)-erogorgiaene and its C-11 epimer is reported. The key stereochemistry controlling steps involve catalytic asymmetric crotylation, anionic oxy-Cope rearrangement and cationic cyclisation. (-)-Erogorgiaene exhibited promising antitubercular activity against multidrug-resistant strains of Mycobacterium tuberculosis.
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The Mechanism of Inhibition of Mycobacterial (p)ppGpp Synthetases by a Synthetic Analog of Erogorgiaene.
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The synthesis of (p)ppGpp alarmones plays a vital role in the regulation of metabolism suppression, growth rate control, virulence, bacterial persistence, and biofilm formation. The (p)ppGpp alarmones are synthesized by proteins of the RelA/SpoT homolog (RSH) superfamily, including long bifunctional RSH proteins and small alarmone synthetases. Here, we investigated enzyme kinetics and dose-dependent enzyme inhibition to elucidate the mechanism of 4-(4,7-dimethyl-1,2,3,4-tetrahydronaphthalen-1-yl)pentanoic acid (DMNP) action on the (p)ppGpp synthetases Rel and RelZ from Mycolicibacterium smegmatis and Rel from Mycobacterium tuberculosis.
View Article and Find Full Text PDFTotal Synthesis of (+)-Erogorgiaene and the Pseudopterosin A-F Aglycone via Enantioselective Cobalt-Catalyzed Hydrovinylation.
Chemistry
August 2021
University of Cologne, Greinstrasse 4, 50939, Koeln, Germany.
Due to their pronounced bioactivity and limited availability from natural resources, metabolites of the soft coral Pseudopterogorgia elisabethae, such as erogorgiaene and the pseudopterosines, represent important target molecules for chemical synthesis. We have now developed a particularly short and efficient route towards these marine diterpenes exploiting an operationally convenient enantioselective cobalt-catalyzed hydrovinylation as the chirogenic step. Other noteworthy C-C bond forming transformations include diastereoselective Lewis acid-mediated cyclizations, a Suzuki coupling and a carbonyl ene reaction.
View Article and Find Full Text PDFAsymmetric Total Synthesis of (-)-Erogorgiaene and Its C-11 Epimer and Investigation of Their Antimycobacterial Activity.
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Department of Chemistry, Loughborough University, Loughborough, LE11 3TU, UK.
A short, nine-step, highly enantioselective synthesis of (-)-erogorgiaene and its C-11 epimer is reported. The key stereochemistry controlling steps involve catalytic asymmetric crotylation, anionic oxy-Cope rearrangement and cationic cyclisation. (-)-Erogorgiaene exhibited promising antitubercular activity against multidrug-resistant strains of Mycobacterium tuberculosis.
View Article and Find Full Text PDFThe combined C-H functionalization/Cope rearrangement: discovery and applications in organic synthesis.
Acc Chem Res
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Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.
The development of methods for the stereoselective functionalization of sp(3) C-H bonds is a challenging undertaking. This Account describes the scope of the combined C-H functionalization/Cope rearrangement (CHCR), a reaction that occurs between rhodium-stabilized vinylcarbenoids and substrates containing allylic C-H bonds. Computational studies have shown that the CHCR reaction is initiated by a hydride transfer to the carbenoid from an allyl site on the substrate, which is then rapidly followed by C-C bond formation between the developing rhodium-bound allyl anion and the allyl cation.
View Article and Find Full Text PDFTotal synthesis of (+)-erogorgiaene using lithiation-borylation methodology, and stereoselective synthesis of each of its diastereoisomers.
J Am Chem Soc
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School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, United Kingdom.
A short (8 steps) synthesis of (+)-erogorgiaene in 44% overall yield from p-methylacetophenone is described. Key steps include lithiation/borylation-protodeboronation to build up the molecule and control the stereochemistry at C1 and C4. The C11 stereochemistry was similarly set up by using lithiation/borylation methodology.
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