The Pd-catalyzed TBHP-mediated Wacker-type oxidation of internal alkenes is reported. The reaction uses 2-(4,5-dihydro-2-oxazolyl)quinoline (Quinox) as ligand and TBHP(aq) as oxidant to deliver single ketone constitutional isomer products in a predictable fashion from electronically biased olefins. This methodology is showcased through its application on an advanced intermediate in the total synthesis of the antimalarial drug artemisinin.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3615722 | PMC |
| http://dx.doi.org/10.1021/jo302638v | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
The utilization of Pd(ii)-catalyzed oxidation for the transformation of terminal olefins into methyl ketones has emerged as a particularly intriguing and versatile strategy in organic synthesis. Herein we report a novel Pd(ii)-catalyzed Wacker-type oxidation with covalent bidentate ligands. The ligand, 1-(pyridin-2-yl)-1,2-dihydro-3-indazol-3-one, exhibits excellent performance in converting olefins to ketones.
View Article and Find Full Text PDFZeolite-Encaged Isolated Palladium Redox Centers toward Sustainable Wacker-Type Oxidations.
J Am Chem Soc
October 2024
Key Laboratory of Advanced Energy Materials Chemistry of Ministry of Education, College of Chemistry, Nankai University, Tianjin 300071, P. R. China.
The selective oxidation of olefins by molecular oxygen holds great importance in the chemical industry due to its remarkable adaptability in constructing carbonyl compounds. Classical homogeneous Wacker oxidation with a complex system of PdCl-CuCl-HO is currently employed in the industrial production of acetaldehyde, which suffers from several key drawbacks. The development of alternative heterogeneous catalytic systems for Wacker-type oxidations has been hotly pursued for decades.
View Article and Find Full Text PDFChemical and Redox Noninnocence of Pentane-2,4-dione Bis(-methylisothiosemicarbazone) in Cobalt Complexes and Their Application in Wacker-Type Oxidation.
JACS Au
March 2024
University of Vienna, Institute of Inorganic Chemistry, Währinger Strasse 42, A-1090 Vienna, Austria.
Article Synopsis
- Cobalt complexes with specific ligands like PBIT are being studied for their potential in complex catalytic processes.
- Various methods such as spectroscopy and computational calculations were used to investigate the properties and redox behavior of these complexes.
- Two specific cobalt complexes showed promise as precatalysts for a Wacker-type oxidation reaction, with insights into their mechanisms and the critical role of phenylsilane and the special characteristics of PBIT.
Enantioselective total synthesis of (‒)-lucidumone enabled by tandem prins cyclization/cycloetherification sequence.
Nat Commun
March 2024
State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences & Peking Union Medical College, 100050, Beijing, P. R. China.
The Ganoderma meroterpenoids are a growing class of natural products with architectural complexity, and exhibit a wide range of biological activities. Here, we report an enantioselective total synthesis of the Ganoderma meroterpenoid (‒)-lucidumone. The synthetic route features several key transformations, including a) a Cu-catalyzed enantioselective silicon-tethered intramolecular Diels-Alder cycloaddition to construct the highly functionalized bicyclo[2.
View Article and Find Full Text PDFElectrochemical aerobic Wacker-type oxygenation of triaryl substituted alkenes to 1,2,2-triarylethanones.
Chem Commun (Camb)
March 2024
School of Chemical Engineering & Technology, China University of Mining and Technology, Xuzhou 221116, Jiangsu, P. R. China.
Article Synopsis
- * This is the first time Wacker-type oxidation has been applied to trisubstituted alkenes and the process does not require transition metals, making it versatile across different functional groups.
- * The reaction occurs under mild conditions and produces good yields, with the mechanism involving a C=O bond formation through interactions between carbon cations and superoxide radicals, aided by a 1,2-shift of an electron-rich substituent.
Want 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!