Reductive deoxygenation of alcohols is particularly challenging because of the high bond dissociation energy of the C-OH bond and the poor leaving ability of the hydroxyl group. Herein we describe a PhP═O-catalyzed reductive deoxygenation of benzyl alcohols with PhSiH under an air atmosphere within 30 min of reaction time. The use of catalytic loading of PhP═O enhances the practicality of this protocol.
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http://dx.doi.org/10.1021/acs.joc.4c01847 | 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 PDFNat Commun
January 2025
Flow Chemistry Group, Van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Amsterdam, The Netherlands.
Secondary amines are vital functional groups in pharmaceuticals, agrochemicals, and natural products, necessitating efficient synthetic methods. Traditional approaches, including N-monoalkylation and reductive amination, suffer from limitations such as poor chemoselectivity and complexity. Herein, we present a streamlined deoxygenative photochemical alkylation of secondary amides, enabling the efficient synthesis of α-branched secondary amines.
View Article and Find Full Text PDFMolecules
December 2024
Graduate School of Science and Engineering, Kagoshima University, 1-21-40 Korimoto, Kagoshima 890-0065, Japan.
In recent years, increased attention has been given to the effective use of chitin nanofibers (ChNFs). We have developed a method to fabricate thinner chitin nanomaterials, called scale-down chitin nanofibers (SD-ChNFs), by a bottom-up procedure at the nanoscale level, with subsequent disintegration by electrostatic repulsion. The surface modification of SD-ChNFs is anticipated to provide new properties and functions for their practical applications.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Département de chimie, Université de Montréal, Montréal, Québec, Canada, H3C 3J7.
Compounds featuring bonds between mercury and transition metals are of interest for their intriguing/ambiguous bonding and scarcely explored reactivities. We report herein the synthesis and reactivities of the new compound [(POCOP)Ni]Hg, [NiHg], featuring a trinuclear Ni-Hg-Ni core (POCOP=κ,κ,κ-2,6-(i-PrPO)CH). [NiHg] reacts with CO to give the carbonate-bridged complex [NiCO].
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
School of Chemistry and Chemical Engineering, Henan Key Laboratory of Boron Chemistry and Advanced Materials, Henan Normal University, Xinxiang, Henan453007,China.
Borenium ions have attracted significant attention in organic transformations due to their strong Lewis acidity. The reported borenium ions are often stabilized by sterically demanding substituents and strong coordination bonds. Herein, we have synthesized a small steric borenium-equivalent NHBHOTf and subjected it to the exhaustive reduction of a carboxylic functional group to a methyl group, which shows broad functional group tolerance.
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