Supercritical carbon dioxide (scCO2) is an effective reaction medium to perform the oxidation of primary and secondary aliphatic alcohols to the corresponding carbonyl compounds with chromium trioxide supported on silica. These reactions were performed by flowing a solution of the alcohol in scCO2 through a column containing the supported reagent and recovering the product by depressurization. This method avoids the use of organic solvents and the contamination of the products with chromium species.
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Sci Adv
January 2025
State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China).
Singly occupied molecular orbital (SOMO) activation of in situ generated enamines has achieved great success in (asymmetric) α-functionalization of carbonyl compounds. However, examples on the use of this activation mode in the transformations of other functional groups are rare, and the combination of SOMO activation with transition metal catalysis is still less explored. In the area of deoxygenative functionalization of amides, intermediates such as iminium ions and enamines were often generated in situ to result in the formation of α-functionalized amines.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China.
ConspectusThe Mannich reaction, involving the nucleophilic addition of an enol(ate) intermediate to an imine or iminium ion, is one of the most widely used synthetic methods for the synthesis of β-amino carbonyl compounds. Nevertheless, the homo-Mannich reaction, which utilizes a homoenolate intermediate as the nucleophilic partner and provides straightforward access to the valuable γ-amino carbonyl compounds, remains underexplored. This can be largely attributed to the difficulties in generation and manipulation of the homoenolate species, despite various homoenolate equivalents that have been developed.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Engineering Research Center of Organosilicon Compounds & Materials (Ministry of Education), Hubei Key Lab on Organic and Polymeric OptoElectronic Materials, College of Chemistry and Molecular Sciences, and TaiKang Center for Life and Medical Sciences, Wuhan University, Wuhan 430072, China.
A modular platform technology for the synthesis of α-aryl carbonyl derivatives via Borono-Catellani-type secondary alkylation of arenes is presented. This practical method features a broad substrate scope regarding aryl boronic acid catechol esters, secondary alkyl bromides, and diversified terminating reagents (e.g.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Shanghai Jiao Tong University, Chemistry, 800 Dongchuan Road, Minhang, 200240, Shanghai, CHINA.
Hydrogen sulfide (H2S) plays crucial inflammatory modulating roles, representing a promising candidate for anti-inflammatory therapies. However, current H2S delivery approaches lack sufficient specificity against inflammatory response. Herein, regarding the overexpressed aminopeptidase N (APN) at the inflammation sites, an APN-activated self-immolative carbonyl sulfide (COS)/H2S donor (AlaCOS) was developed for inflammatory response-specific H2S delivery.
View Article and Find Full Text PDFAn Acad Bras Cienc
January 2025
Universidade Federal do Pará, Instituto de Ciências Exatas e Naturais, Laboratório de Investigação Sistemática em Biotecnologia e Biodiversidade Molecular, Rua Augusto Corrêa, 01, 66075-110 Belém, PA, Brazil.
In the present study, 5-Hydroxy-2-(Oleoyloxymethyl) -4H-pyran-4-one (KMO 3), and their chelated with Cu(II) and Fe(III) ions were synthesized to explore their inhibitory activity against tyrosinase and cytotoxicity. To this end, the structures of the obtained compounds were confirmed by ATR/FT-IR, 13C and 1H-NMR, and UV-vis techniques. The results show that chelating fatty ester presents the bands at 1567m, 1511w cm-1 attributed to the coordinated carbonyl (Cu(II)←[O=C]2), and the bands at 1540m, 1519m cm-1 which were attributed to the coordinated carbonyl (Fe(III)←[O=C]3).
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