Assignment of the liposidomycin diazepanone stereochemistry.
The liposidomycins comprise a family of complex nucleoside antibiotics that inhibit bacterial peptidoglycan synthesis. Their structures (1, 2) feature nucleoside, ribofuranoside, diazepanone, and lipid regions. Several stereogenic centers remain unassigned, including three within the diazepanone region: C-6', C-2'", and C-3'". An intramolecular reductive amination reaction has been used to prepare model diazepanones. Analysis of 40 and two of its diastereomers by NMR spectroscopy, X-ray crystallography, and molecular modeling indicates a close relative configurational and conformational match between 40 and the liposidomycin diazepanone degradation product 43 and allows the assignment of stereochemistry of the natural products as either [C-6'(R), C-2'"(R), C-3'"(R)] or [C-6'(S), C-2'"(S), C-3'"(S)].
Knapp
S
S
Department of Chemistry & Chemical Biology, Rutgers - The State University of New Jersey, P.O. Box 939, Piscataway, New Jersey 08854-8087, USA. knapp@rutchem.rutgers.edu
Morriello
G J
GJ
Nandan
S R
SR
Emge
T J
TJ
Doss
G A
GA
Mosley
R T
RT
Chen
L
L
D000586:Amination; D000617:Aminoglycosides; D000900:Anti-Bacterial Agents / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D014633:Valine / Q000031:analogs & derivatives / Q000737:chemistry
D000617:Aminoglycosides; D000900:Anti-Bacterial Agents; C047544:liposidomycins; D014633:Valine