The reductive cleavage of the C-O bonds of aryl ethers has great potential in organic synthesis. Although several catalysts that can promote the reductive cleavage of aryl ethers have been reported, all such systems require the use of an external reductant, , hydrosilane or hydrogen. Here, we report the development of a new nickel-based catalytic system that can cleave the C-O bonds of ethers in the absence of an external reductant. The hydrogen atom required in this new reductive cleavage reaction is provided by the alkoxy group of the substrate, which serves as an internal reductant. The absence of an external reductant enables the unique chemoselectivity, , the selective reduction of an alkoxy group over alkenes and ketones.
Download full-text PDF |
Source |
---|---|
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5659071 | PMC |
http://dx.doi.org/10.1039/c5sc00305a | DOI Listing |
Org Lett
January 2025
School of Environmental and Chemical Engineering, Wuyi University, Jiangmen 529090, P. R. China.
We have realized a cathodic deoxygenative alkylation between nitro(hetero)arenes and organic halides, employing bis(pinacolato)diboron (Bpin) and LiCl as additives to trap and stabilize the generated alkyl radicals and carbanions, thereby facilitating efficient N-O cleavage and selective C-N bond formation. The protocol offers an economical method for the efficient synthesis of multiple aromatic(hetero) amines, without the need for reactive reductants and the exclusion of air and moisture. Notably, the protocol is distinguished by scalability, broad functional group compatibility, and safe and mild conditions, demonstrating practicality in the synthesis and late-stage modification of various bioactive compounds.
View Article and Find Full Text PDFNanomaterials (Basel)
January 2025
School of Sciences and Humanities, Nazarbayev University, Astana 010000, Kazakhstan.
Doxorubicin (DOX) is one of the most widely used chemotherapy drugs in the treatment of both solid and liquid tumors in patients of all age groups. However, it is likely to produce several side effects that include doxorubicin cardiomyopathy. Nanoparticles (NPs) can offer targeted delivery and release of the drug, potentially increasing treatment efficiency and alleviating side effects.
View Article and Find Full Text PDFChemistry
January 2025
Centre CEA Paris-Saclay: Commissariat a l'Energie Atomique et aux Energies Alternatives Centre de Saclay, IRAMIS Institute, CEA - Saclay, 91190, Gif-Sur-Yvette, FRANCE.
The Schwartz's reagent Cp2Zr(H)Cl is a well known stoichiometric reagent for the reduction of unsaturated organic molecules but it has rarely been used in catalytic transformations. Herein, we describe the reduction of a variety of organic carbonates using the catalyst Cp2Zr(H)Cl in combination with Me(MeO)2SiH (DMMS) as reductant. This method was further applied to the reductive depolymerization of some polycarbonate materials and yielded silylated alcohols and diols in mild conditions.
View Article and Find Full Text PDFChem Sci
January 2025
State Key Laboratory of Physical Chemistry of Solid Surfaces and Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry College of Chemistry and Chemical Engineering, Xiamen University Xiamen 361005 China
Lytic polysaccharide monooxygenases (LPMOs) are a unique group of monocopper enzymes that exhibit remarkable ability to catalyze the oxidative cleavage of recalcitrant carbohydrate substrates, such as cellulose and chitin, by utilizing O or HO as the oxygen source. One of the key challenges in understanding the catalytic mechanism of LPMOs lies in deciphering how they activate dioxygen using diverse reductants. To shed light on this intricate process, we conducted in-depth investigations using quantum mechanical/molecular mechanical (QM/MM) metadynamics simulations, molecular dynamics (MD) simulations, and density functional theory (DFT) calculations.
View Article and Find Full Text PDFSmall Methods
January 2025
State Key Laboratory of Green Pesticide, Key Laboratory of Green Pesticide & Agricultural Bioengineering, Ministry of Education, State-Local Joint Laboratory for Comprehensive Utilization of Biomass, Center for R&D of Fine Chemicals, Guizhou University, Guiyang, Guizhou, 550025, China.
Photocatalytic transfer hydrogenation of biomass-derived aldehydes to alcohols often results in unwanted coupling co-products. Herein, an ultraselective hydrogen transfer system enabled by in situ oxidative C─C bond cleavage over a Janus single-atom palladium on titanium dioxide (0.5Pd/TiO) photocatalyst is presented.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!