Enantioselective total synthesis of otteliones A and B was accomplished. The key steps are radical cyclization of an alpha-iodoketone to construct the cis-hydrindanone skeleton and Suzuki-Miyaura coupling to incorporate the aromatic group. (+)-Ottelione A was converted to (-)-ottelione B on treatment with NaOH in THF.
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http://dx.doi.org/10.1021/ol902776d | DOI Listing |
J Am Chem Soc
January 2025
BioCIS, Faculté de Pharmacie, Université Paris-Saclay, CNRS, Orsay 91400, France.
The endoperoxide scaffold is found in numerous natural products and synthetic substances of pharmaceutical interest. The main challenge to their synthetic access remains the preparation of chiral compounds due to the weakness of the peroxide bond, which limits the scope of available or applicable methods. Here, we demonstrate how peroxycarbenium species can be trapped by silylated nucleophiles with high enantioselectivities and diastereoselectivities when applicable, using a chiral imidophosphorimidate (IDPi) as a catalyst.
View Article and Find Full Text PDFChirality
January 2025
State Key Laboratory of Food Science and Resources, Jiangnan University, Wuxi, Jiangsu, China.
Efficient enantioselective separation is a critical process in pharmaceutical and chemical industries for the production of chiral compounds. Herein, we developed a novel approach for the efficient enantioselective separation of primary amines using supercritical fluid chromatography (SFC) with a commercially available SFC column, Cel1. The key factors of separation, including cosolvent ratios, total cosolvent percentages, and temperature, were systematically assessed in this study.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Jilin Province Key Lab of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun, Jilin, 130022, China.
A modular approach was developed for the first catalytic asymmetric total syntheses of naturally occurring C terpene quinone methides and their non-natural stereoisomers, which feature the presence of an unprecedented spiro[4.4]nonane-containing 6-6-6-5-5-3 hexacyclic skeleton. Resting on a chiral phosphinamide-catalyzed enantioselective reduction of 2,2-disubstituted cyclohexane-1,3-dione, a concise route for the synthesis of enantioenriched 6-6 bicyclic fragment was developed.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
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.
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