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

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 ¹ H and ¹³ C 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.