Synthetic studies towards the tunicamycins and analogues based on diazo chemistry. Total synthesis of tunicaminyl uracil.
A synthetic approach to the tunicamycins, a complex family of nucleosides with potent antibiotic and antiviral activities is reported based on diazo chemistry. The corresponding precursors for the synthesis of tunicaminyl uracil derivatives, the non-stabilized diazo derived from 13 and the aldehyde derivative of uridine, compound 4, were prepared efficiently from commercially available D-galactal and uridine, respectively. After a high yielding coupling reaction to obtain the ketone 14, a stereoselective reduction provided the corresponding tunicaminyl uracil derivative 17a and its C-7 epimer 17b. The interconversion of the diazo and aldehyde functional groups in the requisite building blocks was similarly achieved to obtain the ketone 32, which after reduction yielded the corresponding 7-deoxy-6-hydroxy tunicaminyl uracil analogs 33a and 33b.
Sarabia
Francisco
F
Departamento de Bioquímica, Biología Molecular y Química Orgánica, Facultad de Ciencias, Universidad de Málaga, 29071, Málaga, Spain.
Martín-Ortiz
Laura
L
López-Herrera
F Jorge
FJ
D001391:Azo Compounds / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D014415:Tunicamycin / Q000138:chemical synthesis*
D001391:Azo Compounds; D014415:Tunicamycin