Two syntheses of 3-amino-3-deoxy-α-d-altropyranosyl 3-amino-3-deoxy-α-d-altropyranoside, a new analog of α,α-trehalose, involing reduction of a diazide and reductive amination of a diketone
1986; Elsevier BV; Volume: 157; Linguagem: Inglês
10.1016/0008-6215(86)85060-1
ISSN1873-426X
Autores Tópico(s)Free Radicals and Antioxidants
ResumoA new diamino sugar, 3-amino-3-deoxy-α-d-altropyranosyl 3-amino-3-deoxy-α-d-altropyranoside (5) was synthesized by two routes starting from α,α-threhalose. The first route involved reduction and deprotection of a previously described, benzylidenated diazido analog. The second approach proceeded from the known 2,2′-di-O-benzyl-4,6;4′,6′-bis-O-benzylidene derivative of α-d-altropyranosyl α-d-altropyranoside, to the corresponding 3,3′-diketone, which was subjected to reductive amination with sodium cyanoborohydride and ammonium acetate. The major product, separated in 39% yield from by-products after N-acetylation, was deprotected to give 5. Four by-products were isolated in low yields and determined to be monoaminated analogs which comprise two epimeric, 3′-hydroxy structures and two 3′-epimeric, 3′-cyano-3′-hydroxy structures in their non-aminated residues. A number of observations concerning the 13C- and 1H-n.m.r. spectra of the products are discussed, especially with regard to chemical-shift dependencies for certain ring and substituent protons, and attention is drawn to some inter-residue shielding phenomena.
Referência(s)