Enantioselective total syntheses and X-ray structures of both (S)-tetrahydropalmatrubine (2) and (S)-corytenchine (3) are reported for the first time. They were both derived from (S)-N-norlaudanidine, a benzyltetrahydroisoquinoline that was synthesized with high (>95% ee) enantioselectivity using a chiral auxiliary-assisted Bischler-Napieralski cyclization/reduction approach.
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http://dx.doi.org/10.1021/np1001169 | DOI Listing |
J Am Chem Soc
December 2024
State Key Laboratory of Chemical Biology, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
Here, we report the enantioselective total syntheses of four diepoxy--kaurane diterpenoids including (-)-Macrocalin B, (-)-Acetyl-macrocalin B, and (-)-Isoadenolin A and the revised structure of (-)-Phyllostacin I, which hinges on the strategic design of a regioselective and stereospecific trapping of a highly reactive [3.2.1]-bridgehead enone intermediate via a tethered intramolecular Diels-Alder reaction.
View Article and Find Full Text PDFPhys Rev Lett
December 2024
Institute of Precision Optical Engineering, School of Physics Science and Engineering, Tongji University, Shanghai 200092, China.
Harnessing chiral optical forces facilitates numerous applications in enantioselective sorting and sensing. To date, significant challenges persist in substantiating the holistic complex theorem of these forces as experimental demonstrations employ common light waves (e.g.
View Article and Find Full Text PDFChemistry
December 2024
Organocatalysis Research Group, Institute of Organic Chemistry, HUN-REN Research Centre for Natural Sciences, 2. Magyar tudósok krt., H-1117, Budapest, Hungary.
A concise, bioinspired, and enantioselective synthesis of (-)-hunterine A, an odd 6/7/6/6/5 pentacyclic natural product, is described. The key step in the synthesis of this complex structure is an interim-template directed 6-exo selective epoxide ring-opening reaction, which is interwoven with a hydrolysis step of the indolenine hemiaminal template to create the unusual 7-membered azepine bridge motif. Our work not only refines the previously proposed biogenetic pathway, but also reveals the possible stereochemical prerequisite of the unique skeletal rearrangement, which provides a vantage point for understanding how (-)-hunterine A is likely to be generated in nature.
View Article and Find Full Text PDFChemistry
December 2024
Department of Organic Chemistry and Center for Molecular Biosciences, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria.
We present a comprehensive account on the evolution of a synthetic platform for a subfamily of ent-pimaranes. For the most complex member, norflickinflimiod C, five distinct strategies relying on either cationic or radical polyene cyclizations to construct the requisite tricyclic carbon scaffold were explored. Insights from early and late stage oxidative and reductive dearomatization studies ultimately led to a mild, rhodium-catalyzed arene hydrogenation for the final synthetic route.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Hubei Research Center of Fundamental Science-Chemistry, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, China.
The "Magic Methyl" effect has received tremendous interest in medicinal chemistry due to the significant pharmacological and physical modification of properties that have been observed upon introducing a methyl group, especially, a stereogenic methyl group into potential chiral drug candidates. The prevalence of stereogenic β-methyl ketone structural motifs in bioactive compounds and natural products has long motivated the development of enantioselective strategies toward their synthesis. Herein, we have rationally designed a Rh-catalyzed asymmetric monohydrogenation of readily-available β'-methylene conjugated enones with high efficiency and remarkable site-selectivity and enantioselectivity control for the practical construction of enantioenriched β'-methyl unsaturated enones that are difficult to access by other methods.
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