Advanced search
1 file | 1.15 MB

Synthesis of 1,4-oxazepane-2,5-diones via cyclization of rotationally restricted amino acid precursors and structural reassignment of serratin

Ewout Ruysbergh (UGent) , Kristof Van Hecke (UGent) , Christian Stevens (UGent) , Norbert De Kimpe (UGent) and Sven Mangelinckx (UGent)
(2017) JOURNAL OF ORGANIC CHEMISTRY. 82(12). p.6210-6222
Author
Organization
Abstract
Several natural products containing a 1,4-oxazepane-2,5-dione-core are known. One example is serratin, isolated from Serratia marcescens. Because of the presence of a carboxylic amide, which has a preference for a trans conformation, and the presence of a labile lactone in this core, many synthetic methodologies commonly used for the cyclization toward medium-sized heterocycles cannot be applied. As N-acyl amino acids lacking a third substituent at nitrogen failed to undergo ring-closure, several N-protecting groups were evaluated. With the use of the removable PMB-group, an N-unsubstituted 1,4-oxazepane-2,5-dione was synthesized. Via the application of pseudoprolines (i.e. serine-derived oxazolidines as another type of protecting group), a compound with the presumed structure of the natural product serratin was obtained. As a result of the differences in spectral data, the incorrect structural assignment of the natural product serratin was identified. Instead of the predicted seven-membered heterocycle, a symmetrical serratamolide analogue is proposed to be the correct structure of serratin.
Keywords
NUCLEAR MAGNETIC RESONANCE, CIS-TRANS ISOMERIZATION, RING-CLOSURE, PEPTIDE-SYNTHESIS, CYCLIC-PEPTIDES, VIBRIO-HARVEYI, DERIVATIVES, SERINE, SERRATAMOLIDE, ANALOGS

Downloads

  • (...).pdf
    • full text
    • |
    • UGent only
    • |
    • PDF
    • |
    • 1.15 MB

Citation

Please use this url to cite or link to this publication:

Chicago
Ruysbergh, Ewout, Kristof Van Hecke, Christian Stevens, Norbert De Kimpe, and Sven Mangelinckx. 2017. “Synthesis of 1,4-oxazepane-2,5-diones via Cyclization of Rotationally Restricted Amino Acid Precursors and Structural Reassignment of Serratin.” Journal of Organic Chemistry 82 (12): 6210–6222.
APA
Ruysbergh, E., Van Hecke, K., Stevens, C., De Kimpe, N., & Mangelinckx, S. (2017). Synthesis of 1,4-oxazepane-2,5-diones via cyclization of rotationally restricted amino acid precursors and structural reassignment of serratin. JOURNAL OF ORGANIC CHEMISTRY, 82(12), 6210–6222.
Vancouver
1.
Ruysbergh E, Van Hecke K, Stevens C, De Kimpe N, Mangelinckx S. Synthesis of 1,4-oxazepane-2,5-diones via cyclization of rotationally restricted amino acid precursors and structural reassignment of serratin. JOURNAL OF ORGANIC CHEMISTRY. 2017;82(12):6210–22.
MLA
Ruysbergh, Ewout et al. “Synthesis of 1,4-oxazepane-2,5-diones via Cyclization of Rotationally Restricted Amino Acid Precursors and Structural Reassignment of Serratin.” JOURNAL OF ORGANIC CHEMISTRY 82.12 (2017): 6210–6222. Print.
@article{8545191,
  abstract     = {Several natural products containing a 1,4-oxazepane-2,5-dione-core are known. One example is serratin, isolated from Serratia marcescens. Because of the presence of a carboxylic amide, which has a preference for a trans conformation, and the presence of a labile lactone in this core, many synthetic methodologies commonly used for the cyclization toward medium-sized heterocycles cannot be applied. As N-acyl amino acids lacking a third substituent at nitrogen failed to undergo ring-closure, several N-protecting groups were evaluated. With the use of the removable PMB-group, an N-unsubstituted 1,4-oxazepane-2,5-dione was synthesized. Via the application of pseudoprolines (i.e. serine-derived oxazolidines as another type of protecting group), a compound with the presumed structure of the natural product serratin was obtained. As a result of the differences in spectral data, the incorrect structural assignment of the natural product serratin was identified. Instead of the predicted seven-membered heterocycle, a symmetrical serratamolide analogue is proposed to be the correct structure of serratin.},
  author       = {Ruysbergh, Ewout and Van Hecke, Kristof and Stevens, Christian and De Kimpe, Norbert and Mangelinckx, Sven},
  issn         = {0022-3263},
  journal      = {JOURNAL OF ORGANIC CHEMISTRY},
  keywords     = {NUCLEAR MAGNETIC RESONANCE,CIS-TRANS ISOMERIZATION,RING-CLOSURE,PEPTIDE-SYNTHESIS,CYCLIC-PEPTIDES,VIBRIO-HARVEYI,DERIVATIVES,SERINE,SERRATAMOLIDE,ANALOGS},
  language     = {eng},
  number       = {12},
  pages        = {6210--6222},
  title        = {Synthesis of 1,4-oxazepane-2,5-diones via cyclization of rotationally restricted amino acid precursors and structural reassignment of serratin},
  url          = {http://dx.doi.org/10.1021/acs.joc.7b00790},
  volume       = {82},
  year         = {2017},
}

Altmetric
View in Altmetric
Web of Science
Times cited: