Synthesis and Structure of D-Glucuronolactone Derived Carboxamides.

5-O-Protected and 1,2-acetonide-protected D-glucurono-6,3-lactone furanosides were converted into novel furano-glucuronamides through treatment with ammonia. Several O3 protections and O5-deprotection routes afford new primary gluconamide derivatives. However, attempted O3-benzylations of O5-protected intermediates led instead to silyl migration (from O5-TDBMS), competitive N-benzylation or reclosure to the lactone are observed as competing processes. This is not seen the using 5-O-PMB protection which the provides the method of choice for obtaining a fully protection-differentiated glucofuranamide. X-ray crystal structures of a fully-protected glucurono-6,3-lactone lactone and a glucuronamide derivatives are reported.