Cytotoxic Anomoian B and Aplyzanzine B, New Bromotyrosine Alkaloids from Indonesian Sponges

Abstract

Two new bromotyrosine derivatives, anomoian B (1) and aplyzanzine B (2), were isolated, respectively, from the organic extracts of a Verongida sponge belonging to the Hexadella genus and from a two-sponge association (Jaspis sp. and Bubaris sp.), both collected off the coast of Indonesia. The planar structure of 1 and 2 was determined by 1D and 2D NMR experiments and by high-resolution mass spectrometry, while their absolute stereochemistry was assigned by comparison with optical rotation values of known bromotyrosines and by chemical degradation. Both compounds showed moderate antiproliferative activity against a panel of different cancer cell lines. Their cytotoxic activity is facilitated through the induction of apoptosis, which is mediated neither by the generation of reactive oxygen species nor by the inhibition of histone deacetylases in these cell lines.

Bioactive Bromotyrosine-Derived Alkaloids from the Polynesian Sponge Suberea ianthelliformis

“…These NMR and mass data showed that compound 7 has one methyl group less than compound 6. Examination of the 1 H NMR and HSQC spectra ( Table 3 ) displayed signals with similar chemical shifts to those reported for the tetrabromotyrosine compounds anomoians A and B, previously isolated from Anomoianthella popeae [ 26 ] (order: Verongiida) and from an unknown species of the genus Hexadella (order: Verongiida) collected in Indonesia [ 27 ]. 2D NMR analysis including COSY, HSQC, and HMBC ( Table 3 , Figure 4 ), allowed identification of the structures of 6 and 7 as the O -demethyl anomoian B and O -demethyl anomoian A, respectively.…”

“…The absolute configuration of the stereocenter C-8 for anomoian C-F ( 6 – 9 ) can be proposed by comparison of the values and signs of their optical rotations in MeOH ([α] +9°, +11°, +7° and +6°, respectively), with the closely related congeners, anomoian A ([α] D +5.1°) [ 26 ], anomoian B ([α] D +10.5°) [ 27 ], iso -Anomoian A ([α] +4.5°) [ 28 ], suberedamines A ([α] +21°) and B ([α] +16°) [ 9 ], indicating that all are bearing l -tyrosine residue. The synthetic iso -Anomoian A ([α] +4.5°) and suberedamines A ([α] +19.5°) allowed the determination of their absolute configurations [ 28 ].…”

Marine natural products

“…The absolute conguration of 1084 was established by a combination of chemical degradation into known compounds along with optical rotation. 439 A small number of purines were reported from Haliclona cymaeformis 1085-1088 (ref. 440) and Clathria strepsitoxa 1089, 1090.…”

Quorum Sensing Inhibitory and Antifouling Activities of New Bromotyrosine Metabolites from the Polynesian Sponge Pseudoceratina n. sp.

“…Setting aside misidentification of organisms and cross-contamination, this reminds us to remain cautious about the use of secondary metabolites for sponge taxonomy [8]. These bromotyrosine derivatives have very diverse structures, from the simplest such as subereaphenols [9], with two bromophenolic units such as psammaplysenes [10][11][12], amomoians [10,13,14], and aplyzanzines [14,15], to the most complex polycyclic such as archerines [16] or fistularins [17]. Among the most recently discovered structures, ma'edamines C and D are characterized by a tetrasubstituted pyridinium moiety, a novelty for this type of compound [18].…”

“…Aplyzanzine A, previously isolated from Aplysina sp. [15], is known for its antibacterial and antifungal activities [53], while aplyzanzine B and other close structures, such as anomoians and psammaplysenes, are mildly cytotoxic against a panel of different cancer cell lines [10,14]. Psammaplysene D, also isolated from a French Polynesian Verongiidae, displayed a substantial inhibition of acetylcholinesterase, probably as an anti-predatory defense through fish antifeedant activity [10].…”