The Diels-Alder reaction of vinylboronates can be easily performed using microwave irradiation giving excellent yields of the cycloadducts. Pinacol vinylboronate was the reagent of choice due to its stability towards hydrolysis, operational simplicity and yields of Diels-Alder products. To the best of our knowledge, this is the first example of microwave-assisted Diels-Alder reaction of boron-substituted dienophiles. Subsequent in situ oxidation of the cycloadducts with alkaline hydrogen peroxide afforded the alcohols efficiently.
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http://dx.doi.org/10.1039/c0ob00020e | DOI Listing |
Mar Drugs
December 2024
Shandong Laboratory of Yantai Drug Discovery, Bohai Rim Advanced Research Institute for Drug Discovery, Yantai 264117, China.
Two new cembrane-derived tricyclic diterpenes belonging to the sarcophytin family, namely 4-hydroxy-chatancin () and sarcotoroid (), together with two known related ones ( and ), were isolated from the soft coral collected off Ximao Island in the South China Sea. The structures of the new compounds were elucidated by extensive spectroscopic analysis, a quantum mechanical nuclear magnetic resonance (QM-NMR) method, a time-dependent density functional theory electronic circular dichroism (TDDFT-ECD) calculation, X-ray diffraction analysis, and comparison with the reported data in the literature. A plausible biosynthetic pathway of compounds - was proposed, involving undergoing a transannular Diels-Alder cycloaddition.
View Article and Find Full Text PDFJ 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 PDFOrg Lett
December 2024
Guangxi Key Laboratory of Natural Polymer Chemistry and Physics, Nanning Normal University, Nanning 530001, P. R. China.
A palladium-catalyzed [2π + 2σ] cycloaddition of vinyl bicyclo[1.1.0]butanes with methyleneindolinones has been developed.
View Article and Find Full Text PDFOrg Lett
December 2024
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, New Cornerstone Science Laboratory, Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Beijing 100190, P. R. China.
Reported herein is the generation of -quinone methides (-QMs) via metal-free visible-light-induced oxidation of -alkylarenols, as well as their subsequent reaction with olefins to afford chromans in good to excellent yields (up to 91%). The key is the selective activation of the benzylic C(sp)-H bond of -alkylarenols via single electron transfer (SET) and the formation of -QMs via hydrogen atom transfer (HAT).
View Article and Find Full Text PDFJ Org Chem
December 2024
College of Biotechnology and Pharmaceutical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, 30 Puzhu Rd S., Nanjing 211816, China.
An electrochemical reductive bimolecular cycloaddition of 2-arylideneindane-1,3-diones has been reported for the synthesis of spirocyclopentanole indane-1,3-diones bearing five contiguous stereocenters with vicinal tetrasubstituted stereocenters, especially involving a quaternary carbon center, in moderate to good yields and excellent diastereoselectivities. The present protocol features mild reaction conditions, no external chemical redox reagents, excellent atom economy, and gram-scale synthesis. In addition, a mechanistic investigation indicates that the reactions proceed through a radical pathway.
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