Dihydropyranone Formation by Ipso C−H Activation in a Glucal 3-Carbamate-Derived Rhodium Acyl Nitrenoid
journal contributionposted on 01.04.2011 by Brisa Hurlocker, Nadia C. Abascal, Lindsay M. Repka, Elsy Santizo-Deleon, Abigail L. Smenton, Victoria Baranov, Ritu Gupta, Sarah E. Bernard, Shenjuti Chowdhury, Christian M. Rojas
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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.