Macrolide fundamental chemistry: sequential conversion of the 14-membered ring macrolide antibiotic oleandomycin to 12- and 10-membered ring macrocyclic lactone systems

Nagel, A.; Celmer, Walter D.; Jefferson, Mark T.; Vincent, Lawrence A.; Whipple, Earl B.; Schulte, Gayle K.

doi:10.1021/jo00376a063

Cited by 13 publications

(5 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The 1 H and 13 C chemical shift values in CDCl 3 were in general agreement with those reported previously. 18 The values for other solvents (DMSO-d 6 , acetone-d 6 , D 2 O buffer) were in accordance with those obtained in CDCl 3 (data deposited as electronic supplementary information †).…”

Section: Assignmentssupporting

confidence: 79%

“…Complete unambiguous assignment of 1 H and 13 C NMR spectra was necessary before performing conformational analysis. 2, 18 . The information about the torsion angles, defining the conformation, was obtained from the vicinal spin-spin coupling constant data and the information about proton-proton spatial proximity was derived from the NOE data.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Conformational analysis of oleandomycin and its 8-methylene-9-oxime derivative by NMR and molecular modelling

et al. 2005

View full text Add to dashboard Cite

Conformations of the 14-membered macrolide antibiotic oleandomycin and its 8-methylene-9-oxime derivative were determined in various solvents. The experimental NMR data--coupling constants and NOE contacts--were compared with the results of molecular modelling--molecular mechanics calculations and molecular dynamics simulations. The conformational changes, on the right-hand side of the 14-membered ring, affected mostly the 3JH2,H3 values and NOE crosspeaks H3 or H4 to H11. Oleandomycin was found to be present predominantly in the C3-C5 folded-in conformations in DMSO-d6 solution, whereas in buffered D2O, acetone-d6 and CDCl3, there was a mixture of folded-in and folded-out conformational families. The predominant conformation of the 8-methylene-oleandomycin-9-oxime derivative in solution was a folded-out one although different amounts of folded-in conformation were also present depending on the solvent. Oleandrose and desosamine sugar moieties adopted the usual and expected chair conformation. The conformation around the glycosidic bonds, governing the relative orientation of sugars vs. the lactone ring, showed a certain flexibility within two conformationally close families. We believe that by combining the experimental NMR data and the molecular modelling techniques, as reported in this paper, we have made significant progress in understanding the conformational behaviour and properties of macrolides. Our belief is based on our own current studies on oleandomycins as well as on the previously reported results and best practices concerning other macrolides. A rational for macrolide conformational studies and advances in methodology has been suggested accordingly.

show abstract

Section: Assignmentssupporting

confidence: 79%

Section: Introductionmentioning

confidence: 99%

Conformational analysis of oleandomycin and its 8-methylene-9-oxime derivative by NMR and molecular modelling

et al. 2005

View full text Add to dashboard Cite

show abstract

“…Basic and acidic translactonizations have also been observed in several ring contractions of natural products …”

Section: 101 Translactonizationsmentioning

confidence: 93%

Macrolactonizations in the Total Synthesis of Natural Products

2006

View full text Add to dashboard Cite

“…Basic and acidic translactonizations have also been observed in several ring contractions of natural products such as oleandomycin or more recently by the use of microwave irradiation to get ring-contracted erythromycin A derivatives . During the synthesis of amphidinolide P, Trost et al employed a distannoxane catalysis to form an intermediate eight-membered lactone from a four-membered one (Scheme ).…”

Section: Macrolactonizations Through “Acid” Activationmentioning

confidence: 99%

“…9 It is also worthy of note that there is one example where an eightmembered lactone could not be isomerized, under various conditions, to the corresponding 15-membered lactone. 82 Basic and acidic translactonizations have also been observed in several ring contractions of natural products such as oleandomycin 679 or more recently by the use of microwave irradiation to get ring-contracted erythromycin A derivatives. 680 During the synthesis of amphidinolide P, Trost et al employed a distannoxane catalysis 681 to form an intermediate eightmembered lactone from a four-membered one (Scheme 59).…”

Section: Macrolactonizations Through the Formation Of An "Activated" ...mentioning

confidence: 99%

Update 1 of: Macrolactonizations in the Total Synthesis of Natural Products

et al. 2013

View full text Add to dashboard Cite

show abstract

Macrolide fundamental chemistry: sequential conversion of the 14-membered ring macrolide antibiotic oleandomycin to 12- and 10-membered ring macrocyclic lactone systems

Cited by 13 publications

References 0 publications

Conformational analysis of oleandomycin and its 8-methylene-9-oxime derivative by NMR and molecular modelling

Conformational analysis of oleandomycin and its 8-methylene-9-oxime derivative by NMR and molecular modelling

Macrolactonizations in the Total Synthesis of Natural Products

Update 1 of: Macrolactonizations in the Total Synthesis of Natural Products

Contact Info

Product

Resources

About