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Keywords = TEMPO/BAIB

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23 pages, 6240 KB  
Review
Piancatelli–Margarita Oxidation and Its Recent Applications in Organic Synthesis
by Marco Bella
Catalysts 2025, 15(8), 780; https://doi.org/10.3390/catal15080780 - 15 Aug 2025
Viewed by 1071
Abstract
Piancatelli–Margarita oxidation is a reaction where primary and secondary alcohols are converted to aldehydes and ketones, respectively. It utilizes TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl), a stable aminoxy radical, as the catalyst and BAIB (bis(acetoxy)iodobenzene), a hypervalent iodine compound, as the stoichiometric oxidant. The reaction proceeds [...] Read more.
Piancatelli–Margarita oxidation is a reaction where primary and secondary alcohols are converted to aldehydes and ketones, respectively. It utilizes TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl), a stable aminoxy radical, as the catalyst and BAIB (bis(acetoxy)iodobenzene), a hypervalent iodine compound, as the stoichiometric oxidant. The reaction proceeds at room temperature, without the need for strong acids, bases, or anhydrous conditions. Mild reaction conditions allow for the chemoselective oxidation of complex and sensitive substrates and the selective oxidation of primary alcohols in the presence of secondary alcohols. The reaction conditions can be controlled to favor the oxidation of primary alcohols to aldehydes or promote the overoxidation of aldehydes to carboxylic acids. This review highlights some recent applications (2020–2025), especially in total synthesis, with special emphasis on large-scale reactions. This review aims to honor the memory of Prof. Piancatelli (1936–2025) and Dr. Roberto Margarita (1970–2016), who developed this reaction. Full article
(This article belongs to the Section Catalysis in Organic and Polymer Chemistry)
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14 pages, 3798 KB  
Article
Oxidation in Flow Using an Ionic Immobilized TEMPO Catalyst on an Ion Exchange Resin
by Johannes Gmeiner and Gerrit A. Luinstra
Catalysts 2024, 14(8), 542; https://doi.org/10.3390/catal14080542 - 19 Aug 2024
Viewed by 2515
Abstract
An ionic heterogenized catalyst system for Anelli oxidation has been developed using potassium 4-sulfonato-oxy-2,2,6,6-tetramethylpiperidine-1-yloxyl (TEMPO-4-sulfate) and anion exchange beads as support material. The catalytic oxidation of benzyl alcohol by bis(acetoxy)iodobenzene (BAIB) in acetonitrile with the modified beads gives a 94% yield of benzaldehyde [...] Read more.
An ionic heterogenized catalyst system for Anelli oxidation has been developed using potassium 4-sulfonato-oxy-2,2,6,6-tetramethylpiperidine-1-yloxyl (TEMPO-4-sulfate) and anion exchange beads as support material. The catalytic oxidation of benzyl alcohol by bis(acetoxy)iodobenzene (BAIB) in acetonitrile with the modified beads gives a 94% yield of benzaldehyde within 60 min (batch operation). The beads give about the same conversion of benzyl alcohol in six consecutive cycles when reused after simple washing, albeit with a somewhat longer half-life time. The TEMPO entity could be removed from the beads using a sodium chloride/sodium hydroxy mixture. Reloading the beads with TEMPO-4-sulfate restored about 80% of their initial catalytic action. This exemplifies that the catalytic activity in a fixed bed can be regained without the need for cleaning and repacking the reactor. Preliminary experiments in a fixed bed show that a constant benzyl alcohol conversion of 84% over 10 residence times (as plug flow) can be achieved by the in-flow execution of the oxidation reaction. Full article
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5 pages, 400 KB  
Short Note
Methyl and Benzyl (Ethyl 3,4-di-O-benzyl-2-O-benzoyl-1-thio-β-d-glucopyranosyl)uronate
by Hannah S. Wootton and Gavin J. Miller
Molbank 2024, 2024(3), M1847; https://doi.org/10.3390/M1847 - 9 Jul 2024
Viewed by 1859
Abstract
Methyl and benzyl (ethyl 3,4-di-O-benzyl-2-O-benzoyl-1-thio-β-D-glucopyranosyl)uronate were synthesised from a protected thioglycoside in three steps. A regioselective ring opening of the benzylidene acetal with BH3.THF generated C6-OH material, which was subsequently oxidised using biphasic TEMPO/BAIB conditions. The [...] Read more.
Methyl and benzyl (ethyl 3,4-di-O-benzyl-2-O-benzoyl-1-thio-β-D-glucopyranosyl)uronate were synthesised from a protected thioglycoside in three steps. A regioselective ring opening of the benzylidene acetal with BH3.THF generated C6-OH material, which was subsequently oxidised using biphasic TEMPO/BAIB conditions. The resultant uronic acid was esterified with either a methyl or benzyl moiety. The products were obtained on a multigram scale and fully characterised by 1H, 13C and 2D NMR, alongside MS and IR analysis. Full article
(This article belongs to the Section Organic Synthesis and Biosynthesis)
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4 pages, 528 KB  
Communication
1,2,3,4-Tetra-O-Acetyl-β-d-Mannuronic Acid
by Laura Beswick and Gavin J. Miller
Molbank 2017, 2017(3), M947; https://doi.org/10.3390/M947 - 14 Jul 2017
Cited by 3 | Viewed by 5349
Abstract
1,2,3,4-Tetra-O-acetyl-β-d-mannuronic acid was synthesized in three steps from commercial d-mannose in 21% yield. Regioselective 6-O-tritylation followed by per-acetylation and 6-OTr removal using HBr/AcOH gave the required primary alcohol substrate, which was then oxidised to the target [...] Read more.
1,2,3,4-Tetra-O-acetyl-β-d-mannuronic acid was synthesized in three steps from commercial d-mannose in 21% yield. Regioselective 6-O-tritylation followed by per-acetylation and 6-OTr removal using HBr/AcOH gave the required primary alcohol substrate, which was then oxidised to the target compound using TEMPO/BAIB. None of the synthetic steps required column chromatography and the product was fully characterized by 1H-NMR, 13C-NMR, 2D NMR, MS and IR. Full article
(This article belongs to the Section Organic Synthesis and Biosynthesis)
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