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Mar Drugs
2021 Aug 03;198:. doi: 10.3390/md19080445.
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Structure and Absolute Configuration of Phenanthro-perylene Quinone Pigments from the Deep-Sea Crinoid Hypalocrinus naresianus.
Vemulapalli SPB
,
Fuentes-Monteverde JC
,
Karschin N
,
Oji T
,
Griesinger C
,
Wolkenstein K
.
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Two new water-soluble phenanthroperylene quinones, gymnochrome H (2) and monosulfated gymnochrome A (3), as well as the known compounds gymnochrome A (4) and monosulfated gymnochrome D (5) were isolated from the deep-sea crinoid Hypalocrinus naresianus, which had been collected in the deep sea of Japan. The structures of the compounds were elucidated by spectroscopic analysis including HRMS, 1D 1H and 13C NMR, and 2D NMR. The absolute configuration was determined by ECD spectroscopy, analysis of J-couplings and ROE contacts, and DFT calculations. The configuration of the axial chirality of all isolated phenanthroperylene quinones (2-5) was determined to be (P). For gymnochrome H (2) and monosulfated gymnochrome A (3), a (2'S,2″R) configuration was determined, whereas for monosulfated gymnochrome D (5) a (2'R,2″R), configuration was determined. Acetylated quinones are unusual among natural products from an echinoderm and gymnochrome H (2) together with the recently reported gymnochrome G (1) represent the first isolated acetylated phenanthroperylene quinones.
Figure 1. Chemical structures of gymnochromes isolated from Hypalocrinus naresianus.
Figure 2. UV/vis (top) and ECD (bottom) spectra (MeOH) of gymnochrome H (2), monosulfated gymnochrome A (3), and monosulfated gymnochrome D (5).
Figure 3. (A) 1H-1H COSY (bold lines) and key 13C-1H HMBC (H→C, OH→C and OH→CO) correlations for gymnochrome H (2). (B) Fully assigned 1H-1H COSY spectrum of gymnochrome H (2). (C,D) Selected regions of 13C-1H HMBC spectrum of gymnochrome H (2) recorded at 280 K highlighting the long-range carbon-proton (2J, 3J, and 4J) correlations that are crucial for the assignment of aromatic carbons. Proton and carbon assignments are shown on the 1D spectra.
Figure 4. Comparison of experimental and calculated ECD curves of gymnochrome H (2) in MeOH. TDDFT ECD calculations were performed on low-energy conformations of 2 at PBE0/def2-tzvpp/def2tzv level of theory.
Figure 5. (A) Crucial ROE contacts for determining the orientation of side chains (yellow lines) shown on the example of a conformer of gymnochrome H (2). (B) A selected region of 2D 1H-1H ROESY spectrum of gymnochrome H (2). Slices extracted through the diagonal peaks of H1a″ and H1b’ (dashed lines) are shown on the right side. Proton assignments are denoted on the resonances.
Figure 6. Newman projections of gymnochrome H (2) (top) and monosulfated gymnochrome D (5) (bottom) with measured J-couplings in Hz. Left projections are along C2′-C1′ and right projections are along C2″-C1″.
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