C-C bond formation by sequential intramolecular hydrogen atom transfer/intermolecular radical allylation reaction in carbohydrate systems

A tandem 1,5-, 1,6- or 1,8-intramolecular hydrogen atom transfer (HAT)/intermolecular radical allylation using mono- or (1→4)-O-disaccharide models is described. It is a simple, sequential, stereocontrolled methodology for C-C bond formation by remote free radical functionalization, giving access to interesting carbohydrate structures carrying differently functionalized tethers. A tandem intramolecular hydrogen atom transfer (HAT)/intermolecular radical allylation is described. This process occurs by a completely regio- and stereoselective route that provides a simple methodology for C-C bond formation on remote positions without modifying the remainder of the carbohydrate.
This work was supported by the Research Programs of the Gobierno de Canarias (SolSubC200801000192 and CTQ2010‐18244) of the Ministerio de Ciencia e Innovación, cofinanced by the Fondo Europeo de Desarrollo Regional (FEDER). I. P.‐M. thanks the Spanish Ministerio de Ciencia e Innovación for the Research Program PIE 200930I138. L. M. Q. thanks the Consejo Superior de Investigaciones Científicas (CSIC) (Program I3P) for fellowships.