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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
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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

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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.
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.
Chicago author-date
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.
Chicago author-date (all authors)
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.
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.
IEEE
[1]
E. Ruysbergh, K. Van Hecke, C. Stevens, N. De Kimpe, and S. Mangelinckx, “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, vol. 82, no. 12, pp. 6210–6222, 2017.
@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},
}

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