Electroreductive ring-opening carboxylation of cycloketone oxime esters with atmospheric carbon dioxide is reported. This reaction proceeded under simple constant current conditions in an undivided cell using glassy carbon as the cathode and magnesium as the sacrificial anode, providing substituted γ- and δ-cyanocarboxylic acids in moderate to good yields. Electrochemically generated cyanoalkyl radicals and cyanoalkyl anion are proposed as the key intermediates.
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http://dx.doi.org/10.1021/acs.joc.2c01816 | DOI Listing |
Inorg Chem
October 2024
College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, P. R. China.
Nanocluster catalysts typically face challenges in balancing stability with catalytic efficiency. This study introduces a unique bismuth-oxo cluster, solely protected by two ring-opened calixarenes, which demonstrates not only enhanced structural stability but also superior catalytic performance in the sustained conversion of CO to HCOOH via electrocatalysis. For the first time, we reveal that under specific solvothermal conditions, -butylcalix[8]arene (TBC[8]) can undergo in situ oxidative cleavage of its C-C bond, leading to ring-opened polyphenolic molecules.
View Article and Find Full Text PDFChem Commun (Camb)
May 2024
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, Dalian University of Technology, Dalian, 116024, China.
Electroreductive ring-opening carboxylation of styrene carbonates with CO to achieve dicarboxylic acids and/or -hydroxy acids has been developed the selective cleavage of the C(sp)-O bond in cyclic carbonates. The product selectivity is probably determined by the stability and reactivity of the key benzylic radical and carbanion intermediate.
View Article and Find Full Text PDFOrg Lett
January 2024
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, Dalian University of Technology, Dalian, Liaoning 116024, People's Republic of China.
Electrocarboxylation of the C(sp)-O bond in 1,3-oxazolidin-2-ones with CO to achieve β-amino acids is developed. The C-O bond in substrates can be selectively cleaved via the single electron transfer on the surface of a cathode or through a CO intermediate under additive-free conditions. A great diversity of β-amino acids can be obtained in a moderate to excellent yield and readily converted to various biologically active compounds.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
June 2023
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China.
Simultaneous electrochemical ring contraction and expansion reactions remain unexplored to date. Herein, the reductive electrosynthesis of heterocycle-fused fulleroids from fullerotetrahydropyridazines and electrophiles in the presence of a trace amount of oxygen has been achieved with concurrent ring contraction and ring expansion. When trifluoroacetic acid and alkyl bromides are employed as electrophiles, heterocycle-fused fulleroids with a 1,1,2,6-configuration are regioselectively formed.
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