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Dihydropyranone formation by ipso C-H activation in a glucal 3-carbamate-derived rhodium acyl nitrenoid.

ABSTRACT: 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.

SUBMITTER: Hurlocker B

PROVIDER: S-EPMC3064709 | biostudies-literature | 2011 Apr

REPOSITORIES: biostudies-literature

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Dihydropyranone formation by ipso C-H activation in a glucal 3-carbamate-derived rhodium acyl nitrenoid.

Hurlocker Brisa B Abascal Nadia C NC Repka Lindsay M LM Santizo-Deleon Elsy E Smenton Abigail L AL Baranov Victoria V Gupta Ritu R Bernard Sarah E SE Chowdhury Shenjuti S Rojas Christian M CM

The Journal of organic chemistry 20110307 7

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. ...[more]

PMID: 21381715

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