Dihydropyranone Formation by Ipso C−H Activation in a Glucal 3-Carbamate-Derived Rhodium Acyl Nitrenoid

By using (N-tosyloxy)-3-O-carbamoyl-d-glucal 10, which removes the need for a hypervalent iodine(III) oxidant, we provide evidence for rhodium nitrenoid-mediated ipso C−H activation as the origin of a C3-oxidized dihydropyranone product 3. This system may be especially susceptible to such a pathway...

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Veröffentlicht in:	Journal of organic chemistry 2011-04, Vol.76 (7), p.2240-2244
Hauptverfasser:	Hurlocker, Brisa, Abascal, Nadia C, Repka, Lindsay M, Santizo-Deleon, Elsy, Smenton, Abigail L, Baranov, Victoria, Gupta, Ritu, Bernard, Sarah E, Chowdhury, Shenjuti, Rojas, Christian M
Format:	Artikel
Sprache:	eng
Schlagworte:	Calcium Gluconate - chemistry Carbamates - chemistry Carbohydrates with 4, 5, 6, ... C atoms, dissacharides and oligosaccharides Carbohydrates. Nucleosides and nucleotides Carbonates - chemistry Catalysis Chemistry Exact sciences and technology Heterocyclic compounds Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives Hydrogen Bonding Kinetics Molecular Structure Organic chemistry Organometallic Compounds - chemistry Oxidants - chemistry Potassium - chemistry Preparations and properties Rhodium - chemistry Tosyl Compounds - chemistry
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Beschreibung
Zusammenfassung:	By using (N-tosyloxy)-3-O-carbamoyl-d-glucal 10, which removes the need for a hypervalent iodine(III) oxidant, we provide evidence for rhodium nitrenoid-mediated ipso C−H activation as the origin of a C3-oxidized dihydropyranone product 3. This system may be especially susceptible to such a pathway because of the ease of forming a cation upon hydride transfer to the rhodium-complexed acyl nitrene.
ISSN:	0022-3263 1520-6904
DOI:	10.1021/jo101599q