Synthesis of phosphonate and phostone analogues of ribose-1-phosphates

• Pitak Nasomjai,
• David O'Hagan and
• Alexandra M. Z. Slawin

Beilstein J. Org. Chem. 2009, 5, No. 37, doi:10.3762/bjoc.5.37

• fluorometabolism in S. cattleya. Keywords: 5-fluoro-5-deoxyribose-1-phosphate; fluorometabolite biosynthesis; phosphonates; phostone; ribose-1-phosphate; Introduction Fluoroacetate (1) and 4-fluorothreonine (2) are unusual secondary metabolites in that they contain a fluorine atom. They are elaborated by the

• step in the biosynthesis involves the fluorinase, an enzyme that catalyses nucleophilic attack of fluoride ion on SAM (3) to generate 5′-FDA (4). The initial fluorinated product 5′-FDA (4) is then depurinated by a purine nucleotide phosphorylase (PNP) to give 5-fluoro-5-deoxyribose-1-phosphate (5

• ). This phosphate intermediate becomes the substrate for a ring opening isomerisation reaction converting 5-fluoro-5-deoxyribose-1-phosphate (5) to 5-fluoro-5-deoxyribulose-1-phosphate (6). Further processing to fluoroacetaldehyde (7) and then conversion to fluoroacetate (1) and 4-fluorothreonine (2