In previous papers, we have described the preparation of chiral building blocks by fragmentation of anomeric alkoxy radicals of carbohydrates. Moreover, nitriles have proven to be extremely versatile functional groups. They may undergo a variety of reactions, especially reduction, alkylation of their enolates, enzymatic hydrolysis to acids and amides by nitrile hydratase, Ritter reaction, and many other synthetically useful transformations.

In this paper, we develop a new protocol for the synthesis of nitriles by β-fragmentation of alkoxy radicals by reaction of β-hydroxy azides with (diacetoxyiodo)benzene (DIB) and iodine. In particular, this reaction has been applied to the synthesis of chiral nitriles by β-fragmentation of anomeric alkoxy radicals from 2-azido-2-deoxy sugars, as shown in Scheme 1.

This work was supported by the Investigation Program no. PB96-1461 of the Dirección General de Investigación Científica y Técnica, Spain. P.M. thanks the Ministerio de Educación y Cultura, Spain, for a fellowship.

2 pages, 1 table, 2 schemes.-- Supporting information available at: http://pubs.acs.org/doi/suppl/10.1021/jo971836w