1571-08-0Relevant articles and documents
Cobalt Corroles as Electrocatalysts for Water Oxidation: Strong Effect of Substituents on Catalytic Activity
Neuman, Nicolás I.,Albold, Uta,Ferretti, Eleonora,Chandra, Shubhadeep,Steinhauer, Simon,R?ner, Paul,Meyer, Franc,Doctorovich, Fabio,Vaillard, Santiago E.,Sarkar, Biprajit
, p. 16622 - 16634 (2020)
Two Co(III) complexes (1Py2 and 2Py2) of new corrole ligands H3L1 (5,15-bis(p-methylcarboxyphenyl)-10-(o-methylcarboxyphenyl)corrole) and H3L2 (5,15-bis(p-nitrophenyl)-10-(o-methylcarboxyphenyl)corrole) with two apical pyridine ligands have been synthesized and thoroughly characterized by cyclic voltammetry, UV-vis-NIR, and EPR spectroscopy, spectroelectrochemistry, single-crystal X-ray diffraction studies, and DFT methods. Complexes 1Py2 and 2Py2 possess much lower oxidation potentials than cobalt(III)-tris-pentafluorophenylcorrole (Co(tpfc)) and similar corroles containing pentafluorophenyl (C6F5) substituents, thus allowing access to high oxidation states of the former metallocorroles using mild chemical oxidants. The spectroscopic (UV-vis-NIR and EPR) and electronic properties of several oxidation states of these complexes have been determined by a combination of the mentioned methods. Complexes 1Py2 and 2Py2 undergo three oxidations within 1.3 V vs FcH+/FcH in MeCN, and we show that both complexes catalyze water oxidation in an MeCN/H2O mixture upon the third oxidation, with kobs (TOF) values of 1.86 s-1 at 1.29 V (1Py2) and 1.67 s-1 at 1.37 V (2Py2). These values are five times higher than previously reported TOF values for C6F5-substituted cobalt(III) corroles, a finding we ascribe to the additional charge in the corrole macrocycle due to the increased oxidation state. This work opens up new possibilities in the study of metallocorrole water oxidation catalysts, particularly by allowing spectroscopic probing of high-oxidation states and showing strong substituent-effects on catalytic activity of the corrole complexes.
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Kawabe et al.
, p. 4210 (1972)
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One-pot conversion of activated alcohols into terminal alkynes using manganese dioxide in combination with the Bestmann-Ohira reagent
Quesada, Ernesto,Taylor, Richard J.K.
, p. 6473 - 6476 (2005)
The direct conversion of activated primary alcohols into terminal alkynes through a sequential one-pot, two-step process involving oxidation with manganese dioxide and then treatment with the Bestmann-Ohira reagent is described. This transformation proceeds efficiently (59-99% yield) under mild reaction conditions with a range of benzylic, heterocyclic and propargylic alcohols. A tandem variant is also described, which is successful only with highly activated substrates.
Synthesis of Carboxamide-Containing Tranylcypromine Analogues as LSD1 (KDM1A) Inhibitors Targeting Acute Myeloid Leukemia
Teresa Borrello, Maria,Benelkebir, Hanae,Lee, Adam,Hin Tam, Chak,Shafat, Manar,Rushworth, Stuart A.,Bowles, Kristian M.,Douglas, Leon,Duriez, Patrick J.,Bailey, Sarah,Crabb, Simon J.,Packham, Graham,Ganesan
, p. 1316 - 1324 (2021)
Lysine-specific demethylase 1 (LSD1/KDM1A) oxidatively removes methyl groups from histone proteins, and its aberrant activity has been correlated with cancers including acute myeloid leukemia (AML). We report a novel series of tranylcypromine analogues with a carboxamide at the 4-position of the aryl ring. These compounds, such as 5 a and 5 b with benzyl and phenethylamide substituents, respectively, had potent sub-micromolar IC50 values for the inhibition of LSD1 as well as cell proliferation in a panel of AML cell lines. The dose-dependent increase in cellular expression levels of H3K4me2, CD86, CD11b and CD14 supported a mechanism involving LSD1 inhibition. The tert-butyl and ethyl carbamate derivatives of these tranylcypromines, although inactive in LSD1 inhibition, were of similar potency in cell-based assays with a more rapid onset of action. This suggests that carbamates can act as metabolically labile tranylcypromine prodrugs with superior pharmacokinetics.
Highly atom efficient synthesis of 2,2,4,5-tetrasubstituted 3(2H)-furanones having both hydroxyl and amino substituents
Antony, Jesna,Mathai, Sindhu,Natarajan, Rakesh,P. Musthafa, Sumi,Rappai, John P.,S. Devaky, Karakkattu
supporting information, (2022/02/25)
We have developed a highly atom efficient synthesis of tetrasubstituted 3(2H)-furanones from easily accessible starting materials such as C,N-diarylaldonitrones and dibenzoylacetylene. Control experiments revealed that reaction of aldonitrones having electron-withdrawing groups on the C-aryl substituent in polar aprotic solvents exhibited high product selectivity while reaction temperature has only a negligible effect on product yield and selectivity.
New method for promoting photosensitive oxidation to remove 1, 2-mercaptoethanol acetal protecting group by utilizing visible light irradiation
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Paragraph 0014-0016, (2021/01/30)
The invention discloses a new method for removing a 1, 2-mercaptoethanol acetal protecting group, and belongs to the field of organic synthetic chemistry. The method comprises the following steps of:under a room-temperature open system, adding a substrate 2-substituted-1, 3-oxo-thio-cyclopentane and a catalytic amount of a photosensitizer Eosin Y into a proper amount of acetonitrile; and performing irradiating with a blue LED lamp for 3 hours while stirring to obtain the corresponding aldehyde compound with favorable yield. The method has the advantages of mild operation conditions, greenness, environmental protection, no harsh water and oxygen removal operation and device, realization of the reaction at room temperature, high substrate conversion rate, simple and easy post-treatment, andprovides a good method for removing the 1, 2-mercaptoethanol acetal protecting group at present.
Method for preparing carbonyl compound by oxidizing alcohol
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Paragraph 0027, (2021/09/08)
The invention provides a method for preparing aldehyde or ketone by alcohol oxidation. Iron nitrate hydrate (Fe (NO) is used as a solvent. 3 )3 · 992 O). 4 - Hydroxyl -2, 2, 6, 6 - tetramethylpiperidine oxide (4 - OH-TEMPO) and carboxylic acid are catalysts, and the alcohol is oxidized to aldehydes or ketones with oxygen or air as an oxidizing agent. Compared with the prior art, water serves as a solvent, so that the pollution-free halogenated hydrocarbon or strong carcinogenic sodium nitrite (NaNO) is avoided. 2 The method is green and environment-friendly, the cost is greatly reduced, and the method is a method suitable for industrial production.
