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Chemoselective α-acylation of tertiary amides proceeded with highly electrophilic acid anhydrides and weak bases under mild conditions. β-Ketoamides containing trifluoroacetyl or perfluoroacyl groups were selectively obtained even in the presence of other functional groups such as ketone, ester, etc. Density functional theory calculations suggest that 1-acyloxyenamine is the key intermediate for the chemoselective α-acylation.
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http://dx.doi.org/10.1021/acs.orglett.3c03719 | DOI Listing |
J Org Chem
September 2025
School of Chemistry and Materials Engineering, Anhui Engineering Research Center for Photoelectrocatalytic Electrode Materials, Huainan Normal University, Huainan, Anhui 232038, P. R. China.
Herein, we report a step- and atom-economical allylation reaction of allyl alcohols with activated alkyl bromides by merging cross-electrophile and dehydroxylative coupling under the catalysis of cobalt. This reaction delivers a method to synthesize multisubstituted γ,δ-unsaturated α,α-difluoro amides and carboxylates in a highly regio- and diastereoselective manner. Furthermore, we also demonstrate the viability of a cobalt-catalyzed cross-electrophile desulfonylative allylation in a proof-of-concept study.
View Article and Find Full Text PDFNat Chem
September 2025
Department of Chemistry and the Trienens Institute for Sustainability and Energy, Northwestern University, Evanston, IL, USA.
Current methods of processing accumulated polyolefin waste typically require harsh conditions, precious metals or high metal loadings to achieve appreciable activities. Here we examined supported, single-site organonickel catalysts for polyolefin upcycling. Chemisorption of Ni(COD) (COD, 1,5-cyclooctadiene) onto Brønsted acidic sulfated alumina (AlS) yields a highly electrophilic Ni(I) precatalyst, AlS/Ni(COD), which is converted under H to the active AlS/NiH catalyst.
View Article and Find Full Text PDFOrg Biomol Chem
September 2025
Shanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology (ECUST), Shanghai 200237, China.
An efficient method for the synthesis of trifluoromethyl-containing vicinal chlorohydrins and dichlorides Mn-mediated chlorohydroxylation and dichlorination of α-(trifluoromethyl)styrenes using NaSO as an oxidant and NaCl as a chlorine source was developed. The distribution of α-hydroxy-α-trifluoromethyl-β-chlorohydrins and α-trifluoromethyl dichlorides was highly dependent on the amount of NaCl and NaSO, as well as the solvent employed. The addition of water would be beneficial for the formation of chlorohydrins.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Department of Chemistry, The University of Hong Kong, Hong Kong 999077, China.
While intricate designs have been implemented to transform noble-metal complexes and sophisticated organic molecules into reactive photocatalysts for the single-electron reduction of unactivated alkyl halides, the development of highly reducing photocatalytic systems based on earth-abundant metals is still in its early stages. Herein, we show that a simple terpyridine-ligated nickel(II) complex, integrated into an imine-linked covalent organic framework, can be readily reduced by photoexcited Hantzsch esters to produce a heterogeneous nickel(I) photocatalyst with a fairly low excited-state oxidation potential of approximately -3.5 V (referenced to the saturated calomel electrode).
View Article and Find Full Text PDFSmall
August 2025
College of Chemistry and Chemical Engineering, Hunan Provincial Key Laboratory of Micro and Nano Material Interface Science, Central South University, Changsha, Hunan, 410083, P. R. China.
The development of a privileged organocatalyst featuring well-defined catalytic sites to drive highly cooperative CO conversion into high value-added fine chemicals is promising while challenging. Here in this work, three zwitterionic betaine-based covalent organic frameworks (COFs) bearing sulfonate, carboxylate, and phosphate moieties, namely, PS-TpBpy, BA-TpBpy, and PA-TpBpy, are in situ engineered through the post-synthetic quaternization of the bipyridine COF (TpBpy). Density functional theory-based Fukui function indicated that the pyridinium cation and the alkaline O anion in these betaine-based COFs serve as synergistic electrophilic and nucleophilic active sites, thus simultaneously activating o-phenylenediamine and CO for their highly efficient conversion to benzimidazole.
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