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. 2009 Apr;72(4):732-8.
doi: 10.1021/np8007649.

Structure elucidation at the nanomole scale. 1. Trisoxazole macrolides and thiazole-containing cyclic peptides from the nudibranch Hexabranchus sanguineus

Doralyn S Dalisay  1 , Evan W Rogers, Arthur S Edison, Tadeusz F Molinski
Affiliations

Structure elucidation at the nanomole scale. 1. Trisoxazole macrolides and thiazole-containing cyclic peptides from the nudibranch Hexabranchus sanguineus

Doralyn S Dalisay et al. J Nat Prod. 2009 Apr.

Abstract

A single specimen of Hexabranchus sanguineus, a nudibranch from the Indo-Pacific that is known to sequester kabiramides B and C and other trisoxazole macrolides, yielded new kabiramide analogues, 9-desmethylkbiramide B and 33-methyltetrahydrohalichondramide, and two new unexpected thiazole-containing cyclic peptides in submicromolar amounts. The structures of these cyclic peptides were determined by analyses of 1D and 2D NMR spectra recorded with a state-of-the-art 1 mm (1)H NMR high-temperature superconducting microcryoprobe, together with mass spectra. In addition to two proline residues, each peptide contains a thiazole- or oxazole-modified amino acid residue, together with conventional amino acid residues. All of the amino acid residues were l, as determined by Marfey's analysis of the acid hydrolysates of the peptides. This is the first report of cyclic thiazole peptides from H. sanguineus. Since thiazole-oxazole-modified peptides are typically associated with cyanobacteria and tunicates, the finding may imply a dietary component of the H. sanguineus that was previously overlooked.

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Figures

Figure 1
Figure 1
X-ray structures of trisoxazoles bound to G-actin (data adapted from Rayment et al. Ref vi. (a) jaspisamide A (6): torsional angles C8(Me)-C8-C9-C10 = −57.4°, H8-C8-C9-H9 =+67.9° (b) kabiramide C (1): torsional angles C8(Me)-C8-C9-C10 = −67.3°, H8-C8-C9-H9 =+75.8° Side chains of each compound (upper left) and protein residues have been removed for clarity
Figure 1
Figure 1
X-ray structures of trisoxazoles bound to G-actin (data adapted from Rayment et al. Ref vi. (a) jaspisamide A (6): torsional angles C8(Me)-C8-C9-C10 = −57.4°, H8-C8-C9-H9 =+67.9° (b) kabiramide C (1): torsional angles C8(Me)-C8-C9-C10 = −67.3°, H8-C8-C9-H9 =+75.8° Side chains of each compound (upper left) and protein residues have been removed for clarity
Figure 2
Figure 2
Subunits of sanguinamide A (7, a) and sanguinamide B (8, b–c), showing 1H-1H COSY and HMBC correlations.
See this image and copyright information in PMC

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