Department of Chemistry, Barnard College, 3009 Broadway, New York, New York 10027, USA.
J Org Chem. 2011 Apr 1;76(7):2240-4. doi: 10.1021/jo101599q. Epub 2011 Mar 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.
通过使用（N-对甲苯磺酰氧基）-3-O-氨甲酰基-D-葡萄糖醛 10，我们去除了高价碘(III)氧化剂的需求，为铑亚硝酰介导的 ipso C-H 活化作为 C3-氧化的二氢吡喃酮产物 3 的起源提供了证据。由于向铑络合的酰基氮烯转移氢化物容易形成阳离子，因此该体系可能特别容易发生这种途径。
