ArticleJournal of the American Chemical Society2014
Copper-catalyzed oxidative dehydrogenative carboxylation of unactivated alkanes to allylic esters via alkenes.
Article in Journal of the American Chemical Society, 2014. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 24 papers.
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24 citing papers in PubMed, 118 citations in OpenAlex.
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- Photoinduced Copper-Catalyzed Enantioselective Allylic C(Journal of the American Chemical Society · 2025Article
- Immobilized Copper Complexes on Coal-Bearing Kaolin for Catalyzing Allylic Ester Synthesis via C(Molecules (Basel, Switzerland) · 2025Article
- Copper-Catalyzed Cyclization and Alkene Transposition Cascade Enables a Modular Synthesis of Complex Spirocyclic Ethers.Journal of the American Chemical Society · 2025Article
- Catalytic undirected methylation of unactivated C(spNature communications · 2024Article
- Dehydrogenative synthesis ofScience advances · 2024Article
- Mechanistic insights into radical formation and functionalization in copper/Chemical science · 2024Article
- Diverse functional polyethylenes by catalytic amination.Science (New York, N.Y.) · 2023Article
- Benzylic C-H Esterification with Limiting C-H Substrate Enabled by Photochemical Redox Buffering of the Cu Catalyst.Journal of the American Chemical Society · 2023Article
- Protocol for chemo- and regioselective C(spSTAR protocols · 2022Article
- Radical C(sp3)-H functionalization and cross-coupling reactions.Nature reviews. Chemistry · 2022Article
- Chemo- and regioselective benzylic C(spiScience · 2022Article
- Metal-free allylic C-H nitrogenation, oxygenation, and carbonation of alkenes by thianthrenation.Chemical science · 2022Article
- Preparation and Degradation of Rhodium and Iridium Diolefin Catalysts for the Acceptorless and Base-Free Dehydrogenation of Secondary Alcohols.Organometallics · 2021Article
- Revealing the Iron-Catalyzed β-Methyl Scission ofMolecules (Basel, Switzerland) · 2020Article
- Effective synthesis of bicyclodienes via palladium-catalyzed asymmetric allylic alkylation and ruthenium-catalyzed cycloisomerization.Turkish journal of chemistry · 2020Article
- Copper-Promoted Functionalization of Organic Molecules: from Biologically Relevant Cu/OChemical reviews · 2019Review
- Challenges and opportunities for alkane functionalisation using molecular catalysts.Chemical science · 2018Review
- Dehydrogenative desaturation-relay via formation of multicenter-stabilized radical intermediates.Nature communications · 2017Article
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3 authors at 2 institutions in 2 countries.
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Abstract
We report copper-catalyzed oxidative dehydrogenative carboxylation (ODC) of unactivated alkanes with various substituted benzoic acids to produce the corresponding allylic esters. Spectroscopic studies (EPR, UV-vis) revealed that the resting state of the catalyst is [(BPI)Cu(O2CPh)] (1-O2CPh), formed from [(BPI)Cu(PPh3)2], oxidant, and benzoic acid. Catalytic and stoichiometric reactions of 1-O2CPh with alkyl radicals and radical probes imply that C-H bond cleavage occurs by a tert-butoxy radical. In addition, the deuterium kinetic isotope effect from reactions of cyclohexane and d12-cyclohexane in separate vessels showed that the turnover-limiting step for the ODC of cyclohexane is C-H bond cleavage. To understand the origin of the difference in products formed from copper-catalyzed amidation and copper-catalyzed ODC, reactions of an alkyl radical with a series of copper-carboxylate, copper-amidate, and copper-imidate complexes were performed. The results of competition experiments revealed that the relative rate of reaction of alkyl radicals with the copper complexes follows the trend Cu(II)-amidate > Cu(II)-imidate > Cu(II)-benzoate. Consistent with this trend, Cu(II)-amidates and Cu(II)-benzoates containing more electron-rich aryl groups on the benzamidate and benzoate react faster with the alkyl radical than do those with more electron-poor aryl groups on these ligands to produce the corresponding products. These data on the ODC of cyclohexane led to preliminary investigation of copper-catalyzed oxidative dehydrogenative amination of cyclohexane to generate a mixture of N-alkyl and N-allylic products.
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