Psammaplysin F, a New Bromotyrosine Derivative from a Sponge, Aplysinella sp.

Abstract

A new member of the psammaplysin family, psammaplysin F (6) has been isolated from an undescribed species of Aplysinella sponge, along with the four known psammaplysins A-C (1-3) and E (5). The structure of psammaplysin F was determined by spectral analysis.

Twilight Zone Sponges from Guam Yield Theonellin Isocyanate and Psammaplysins I and J

“…14, 18-22 Closer inspection of the 13 C NMR data of 5 clearly showed it was characteristic of a psammaplysin skeleton rather than a fistularin, particularly the characteristic resonance for the spiro-carbon C-6 (121.7 ppm). In fact, the C-1 to C-12 part of 5 was found to be identical to that of psammaplysins A ( 7 ) 14 and F. 20 The molecular formula of 5 indicated it differed from 7 by having one less bromine atom in the phenyl ring and from psammaplysin F by missing the same bromine as well as the methyl of the N -CH 3 group. All of the physical and spectroscopic data of 5 supported this deduction, in particular the NOEs between the resonances for H 2 -12 and H-18, and those between H 2 -19 and H-15 and H-17, which confirmed the regio-chemistry of the phenyl ring.…”

Cytotoxic Psammaplysin Analogues from the Verongid Red Sea Sponge Aplysinella Species

“…Members of the order Verongiida are characterized by production of brominated compounds that are biosynthesized from bromotyrosine [1]. Compounds possessing the rare dibrominated 1,6-dioxa-2-azaspiro [4.6]undeca-2,7,9-triene moiety (spirooxepinisoxazoline) are derived from bromotyrosine and are named psammaplysins [2][3][4][5][6][7][8][9][10], ceratinamides [9,11] and ceratinadins [12]. Compounds with the spirooxepinisoxazoline moiety were reported mainly from members of the Verongiida [2][3][4][5][6][7][8][9][10]12] with only two representatives from the order Dictyoceratida [11,13].…”

“…Compounds possessing the rare dibrominated 1,6-dioxa-2-azaspiro [4.6]undeca-2,7,9-triene moiety (spirooxepinisoxazoline) are derived from bromotyrosine and are named psammaplysins [2][3][4][5][6][7][8][9][10], ceratinamides [9,11] and ceratinadins [12]. Compounds with the spirooxepinisoxazoline moiety were reported mainly from members of the Verongiida [2][3][4][5][6][7][8][9][10]12] with only two representatives from the order Dictyoceratida [11,13]. Psammaplysins' backbone consists of two dibrominated subunits, 8,10-dibromo-4-hydroxy-9-methoxy-1,6-dioxa-2-azaspiro [4.6]undeca-2,7,9-triene-3-carboxylic acid (subunit A) and 3-(4-(2-aminoethyl)-2,6-dibromophenoxy)propan-1-amine subunit (subunit B, moloka'iamine) [14], connected together through an amidic linkage between the carboxylic moiety (C-9) of the substituted spirooxepinisoxazoline unit and the terminal amino group at C-10 of the moloka'iamine ( Figure 1) to give the first reported compound of this class, psammaplysin A, (N-(3-(4-(2-aminoethyl)-2,6-dibromophenoxy)propyl)-8,10-dibromo-4-hydroxy-9-methoxy-1,6-dioxa-2azaspiro [4.6]undeca-2,7,9-triene-3-carboxamide) [2].…”

Absolute Configuration and Conformational Study of Psammaplysins A and B from the Balinese Marine Sponge Aplysinella strongylata

“…11 The relative configuration of psammaplysin A (1) was first determined as (6S*,7S*) in 1985 by single-crystal X-ray crystallographic analysis of its diacetyl derivative (2). 3 Subsequent reports on the relative configuration of psammaplysins C−H were made by comparing their specific rotation values with those of psammaplysin A, 4,8,9,11,12 by chemical shift comparisons, [5][6][7]11 or by ROESY/NOESY correlation data. 8−10 The potent biological activities of the psammaplysins, together with their unusual 1,6-dioxa-2-azaspiro [4.6]undeca-2,7,9-triene motif, clearly justify efforts to resolve their absolute configuration, an aspect of their structure elucidation that could not be pursued in the original X-ray crystallographic work due to inferior crystal quality.…”