A reliable method for enone transposition has been developed with the help of silyl group masking. Enantio-switching, substituent shuffling, and -selectivity are the highlights of the method. The developed method was applied for the first total synthesis of peribysin D along with its structural revision. Formal synthesis of -guggulsterone and -volkendousin was also claimed using a short sequence.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.1c02173 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Total Synthesis of the Norcembranoid Scabrolide B and Its Transformation into Sinuscalide C, Ineleganolide, and Horiolide.
J Am Chem Soc
September 2024
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany.
It was recognized only recently that the sister norcembranoids scabrolides A and B have notably different carbotricyclic scaffolds. Therefore, our synthesis route leading to scabrolide A could not be extended to its sibling. Rather, a conceptually new approach had to be devised that relied on a challenging intramolecular alkenylation of a ketone to forge the congested central cycloheptene ring at the bridgehead enone site; the required cyclization precursor was attained by a lanthanide-catalyzed Mukaiyama-Michael addition.
View Article and Find Full Text PDFA practical synthesis of 1,3-disubstituted cubane derivatives.
Chem Commun (Camb)
June 2023
Department of Chemistry, Lancaster University, Bailrigg, LA1 4YB, UK.
A robust multigram-scale synthesis of 1,3-disubstituted cubanes (previously only available on milligram-scale) is reported. The approach exploits a readily available enone intermediate previously used for the synthesis of 1,4-disubstituted cubanes, by introducing a novel Wharton transposition to access useful quantities of 1,3-disubstituted cubanes for diverse applications.
View Article and Find Full Text PDFTwo-Stage Syntheses of Clionastatins A and B.
J Am Chem Soc
May 2022
Department of Chemistry and Key Laboratory of Chemical Biology of Fujian Province, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China.
A concise and divergent synthesis of the polychlorinated marine steroids clionastatin A and B from inexpensive testosterone has been achieved through a unique two-stage chlorination-oxidation strategy. Key features of the two-stage synthesis include (1) conformationally controlled, highly stereoselective dichlorination at C1 and C2 and C4-OH-directed C19 oxygenation followed by a challenging neopentyl chlorination to install three chlorine atoms; (2) desaturation through one-pot photochemical dibromination-reductive debromination and anti-Markovnikov olefin oxidation by photoredox-metal dual catalysis to enhance the oxidation level of the backbone; and (3) Wharton transposition to furnish the D-ring enone. This synthesis proved that the introduction of the C19 chloride in the early stage of the synthesis secured the stability of the backbone against susceptibility to aromatization during the oxidation stage.
View Article and Find Full Text PDFTuning of α-Silyl Carbocation Reactivity into Enone Transposition: Application to the Synthesis of Peribysin D, -Volkendousin, and -Guggulsterone.
Org Lett
September 2021
Organic Chemistry Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411008, India.
A reliable method for enone transposition has been developed with the help of silyl group masking. Enantio-switching, substituent shuffling, and -selectivity are the highlights of the method. The developed method was applied for the first total synthesis of peribysin D along with its structural revision.
View Article and Find Full Text PDF1,3-Alkyl Transposition in Allylic Alcohols Enabled by Proton-Coupled Electron Transfer.
Angew Chem Int Ed Engl
September 2021
Department of Chemistry, Princeton University, Princeton, NJ, 08544, USA.
A method is described for the isomerization of acyclic allylic alcohols into β-functionalized ketones via 1,3-alkyl transposition. This reaction proceeds via light-driven proton-coupled electron transfer (PCET) activation of the O-H bond in the allylic alcohol substrate, followed by C-C β-scission of the resulting alkoxy radical. The transient alkyl radical and enone acceptor generated in the scission event subsequently recombine via radical conjugate addition to deliver β-functionalized ketone products.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!