Structure and Absolute Configuration of Phenanthro-perylene Quinone Pigments from the Deep-Sea Crinoid Hypalocrinus naresianus

Abstract

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.

Insight into the Progress on Natural Dyes: Sources, Structural Features, Health Effects, Challenges, and Potential

“…Lac dyes have been used for textiles and painting for thousands of years [ 22 ]. Recently, some new quinone dyes were isolated from the deep-sea crinoid Hypalocrinus naresianus [ 23 , 24 ]. With the development of marine resources, deep-sea animals are expected to become potential new sources of natural dyes.…”

“…According to the published literature, the study of marine natural products has increasingly captured the attention of scientists in recent years. Some new natural dyes including carotenoids and quinone dyes have been isolated from marine resources [ 23 , 24 , 51 , 77 ]. Additionally, new sources of natural dyes have been found in marine environments, such as a fast-growing strain of Chlorella saccharophila and a new variety of the ridgetail white prawn [ 270 , 271 ].…”

Marine natural products

“…New quinonoid MNPs were reported from crinoids, including naphthopyrones 1479 ( Colobometra perspinosa ) 693 and delicapyrons A–E 1480–1484 ( Comanthus delicata ) 694 and phenanthrol-perylenes gymnochrome H 1485 and gymnochrome A monosulfate 1486 ( Hypalocrinus naresianus ). 695 The porphyrin 1487 was isolated from extracts of the brittle star Ophiura sarsii , representing the first report of the compound as a MNP. 696 The structure proposed for a molecule isolated from the sea urchin Salmacis bicolor was inconsistent with the reported NMR data – the publication should be retracted.…”

A Survey of Recently Discovered Naturally Occurring Organohalogen Compounds

“…49 A collection of the gorgonian Dichotella gemmacea from Weizhou Island in China afforded seven new chlorinated briaranes from 28 new analogues and a total of 39 isolated briaranes. The new chlorine-containing examples are gemmolides R (125), S (126), T (127), U (128), V (129), W (130), and X (131). All of these diterpenoids were examined for their inhibition against the receptor activator of nuclear factor kappa-B ligand (RANKL)-induced osteoclast differentiation in bone marrow macrophages in vitro, but only the known junceellide D shows significant inhibition.…”

“…Interestingly, the enantiomer of natural 280 is even more active (IC 50 4.1 μM). 129 The deep-sea crinoid Hypalocrinus naresianus from Japanese waters is the source of three new gymnochromes, G (281), 130 H (282), 131 and A (283). 131 The triscatecholate siderophore, teredinibactin A (284), was isolated from Teredinibacter turnerae, found living on the shipworm Bankia gouldi.…”