26256-72-4Relevant articles and documents
How Metal Ion Lewis Acidity and Steric Properties Influence the Barrier to Dioxygen Binding, Peroxo O-O Bond Cleavage, and Reactivity
Yan Poon, Penny Chaau,Dedushko, Maksym A.,Sun, Xianru,Yang, Guang,Toledo, Santiago,Hayes, Ellen C.,Johansen, Audra,Piquette, Marc C.,Rees, Julian A.,Stoll, Stefan,Rybak-Akimova, Elena,Kovacs, Julie A.
, p. 15046 - 15057 (2019)
Herein we quantitatively investigate how metal ion Lewis acidity and steric properties influence the kinetics and thermodynamics of dioxygen binding versus release from structurally analogous Mn-O2 complexes, as well as the barrier to Mn peroxo O-O bond cleavage, and the reactivity of Mn oxo intermediates. Previously we demonstrated that the steric and electronic properties of MnIII-OOR complexes containing N-heterocyclic (NAr) ligand scaffolds can have a dramatic influence on alkylperoxo O-O bond lengths and the barrier to alkylperoxo O-O bond cleavage. Herein, we examine the dioxygen reactivity of a new MnII complex containing a more electron-rich, less sterically demanding NAr ligand scaffold, and compare it with previously reported MnII complexes. Dioxygen binding is shown to be reversible with complexes containing the more electron-rich metal ions. The kinetic barrier to O2 binding and peroxo O-O bond cleavage is shown to correlate with redox potentials, as well as the steric properties of the supporting NAr ligands. The reaction landscape for the dioxygen chemistry of the more electron-rich complexes is shown to be relatively flat. A total of four intermediates, including a superoxo and peroxo species, are observed with the most electron-rich complex. Two new intermediates are shown to form following the peroxo, which are capable of cleaving strong X-H bonds. In the absence of a sacrificial H atom donor, solvent, or ligand, serves as a source of H atoms. With TEMPOH as sacrificial H atom donor, a deuterium isotope effect is observed (kH/kD = 3.5), implicating a hydrogen atom transfer (HAT) mechanism. With 1,4-cyclohexadiene, 0.5 equiv of benzene is produced prior to the formation of an EPR detected MnIIIMnIV bimetallic species, and 0.5 equiv after its formation.
EFFECTS OF ADDITIVES ON PHOTO-METHOXYLATION OF METHYL 2-PYRIDINECARBOXYLATE IN ACIDIC METHANOLIC SOLUTIONS. PROMOTION BY 4-SUBSTITUTED PYRIDINES.
Sugimori,Ogishima,Miyazawa,Hasegawa,Suzuki
, p. 1817 - 1821 (1983)
The rate of photo-methoxylation of methyl 2-pyridinecarboxylate(1) in acidic methanol is accelerated by 4-substituted pyridines and their analogs, 4,4 prime -bipyridine and pyrazine. The photo-methoxylation of 1 is not promoted by triplet sensitizers, electron donors, or electron acceptors. Detailed analyses on the 1-4-pyridine-carbonitrile(3) system including wavelength dependence lead to a mechanism for the promotion via an excited complex formed from an excited 1 and 3 in the ground state.
Pd/C-Catalyzed methoxycarbonylation of aryl chlorides
Ai, Han-Jun,Franke, Robert,Wu, Xiao-Feng
, (2020/06/19)
A new protocol for the methoxycarbonylation of aryl chlorides has been developed. Various methyl benzoates were produced in good to excellent yields. Several parameters are crucial for the success of this procedure: 1) the usage of LiOMe as the base or co-nucleophile which facilitate the carbonylative transformation; 2) employing Pd/C as the catalyst to prevent the palladium reduced by MeOH and subsequent agglomerate; 3) CO concentration, excessive CO concentration will directly lead to the termination of the reaction.
FUSED PYRIMIDINE DERIVATIVES HAVING INHIBITORY ACTIVITY ON FMS KINASES
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Page/Page column 34, (2014/01/17)
Disclosed are a fused pyrimidine derivative of formula (I), and a pharmaceutically acceptable salt, stereoisomer, hydrate and solvate thereof, which have an excellent inhibitory activity on FMS kinases, and a pharmaceutical composition comprising the same is effective in preventing or treating diseases caused by abnormal activation of FMS kinases such as immunologic diseases, metabolic diseases, inflammatory diseases, cancers and tumors.