On the Novel Free Porphyrins Corallistin B,C, D,and E: Isolation from the demosponge Corallistes sp. of the Coral Sea and Reactivity of Their Nickel 55 (II) Complexes toward Formylating Reagents

Reported here are the novel free porphyrins corallistin B, C, D, and E, isolated as methyl esters 2a , 3a , 4a , and 5a , respectively, from the sponge Corallistes sp. (Lithistida) collected at the basis of the south New Caledonian coral reef. A protocol is also established for formylation of their Ni^II complexes, which show a different reactivity pattern toward DMF/POCl3 from metal complexes of deuteroporphyrins. Together with corallistin A, Previously isolated as the methyl ester 1a , and the known deuteroporphyrin IX (isolated as 6a ) also present in the sponge, the new corallistins, which may be thought to derive from protoporphyrin via heme, account for an amazing 60% of the EtOh extract from the sponge.     

Validation and evaluation of an HPLC methodology for the quantification of the potent antimitotic compound (+)‐discodermolide in the Caribbean marine sponge Discodermia dissoluta

The sponge Discodermia dissoluta is the source of the potent antimitotic compound (+)‐discodermolide. The relatively abundant and shallow populations of this sponge in Santa Marta, Colombia, allow for studies to evaluate the natural and biotechnological supply options of (+)‐discodermolide. In this work, an RP‐HPLC‐UV methodology for the quantification of (+)‐discodermolide from sponge samples was tested and validated. Our protocol for extracting this compound from the sponge included lyophilization, exhaustive methanol extraction, partitioning using water and dichloromethane, purification of the organic fraction in RP‐18 cartridges and then finally retrieving the (+)‐discodermolide in the methanol–water (80:20 v/v) fraction. This fraction was injected into an HPLC system with an Xterra RP‐18 column and a detection wavelength of 235 nm. The calibration curve was linear, making it possible to calculate the LODs and quantification in these experiments. The intra‐day and inter‐day precision showed relative standard deviations lower than 5%. The accuracy, determined as the percentage recovery, was 99.4%. Nine samples of the sponge from the Bahamas, Bonaire, Curaçao and Santa Marta had concentrations of (+)‐discodermolide ranging from 5.3 to 29.3 μg/g^?1 of wet sponge. This methodology is quick and simple, allowing for the quantification in sponges from natural environments, in situ cultures or dissociated cells.     

Novel Naamidine-Type Alkaloids and Mixed-Ligand Zinc(II) Complexes from a Calcareous Sponge,Leucetta sp., of the Coral Sea

As compounds from a calcareous sponge, Leucetta sp., of the Coral Sea, we isolated a series of novel naamidine-type alkaloids, 6 – 10 , which are oxidized at a single benzylic position. We also report on the first marine, mixed-ligand metal complex 5 and on the first natural metal complexes 3 and 4 derived from classical naamidines, i.e., 1 and 2 . The latter are also present in free form in the sponge.     

Dysidin,ein neuartiger,chlorhaltiger Naturstoff aus dem Schwamm Dysidea herbacea

Dysidin, a novel chlorine containing natural product from the sponge Dysidea herbacea Dysidin ( 1 ) has been isolated from the marine sponge Dysidea herbacea. It structure has been determined by degradation studies and spectroscopic methods. The synthesis of a degradation product is described. The relative and absolute configuration is established by X-ray diffraction methods.     

On the First Marine Stigmastane Sterols and Sterones Having a 24,25-Double Bond. Isolation from the Sponge Stelletta sp. of Deep Coral Sea

The sponge Stelletta sp. (Astrophorida, Stellettidae), collected at ?700 m in the Coral Sea, is shown to contain sterones and sterols of the stigmastane type with a C(24)?C(25) bond for which there is no precedent in the sea. Structure elucidation of the second abundant of these steroids, stigmasta-4,24(25)-dien-3-one ((+)- 1 ), is based on 1D and 2D NMR spectra and chemical transformation to acetate (?)- 5 . Stigmasta-4,24(25)-diene-3,6-dione ((?)- 3 ), present in trace amounts in the sponge, was obtained in sufficient quantity for NMR study by oxidation of the also present, inseparable, and abundant 4:1 mixture of stigmasta-5,24(25)-dien-3β-ol ( 6 ) and its 5,6-dihydro derivative 7 (Scheme 1). This oxidation also afforded the ketone analogues (+)- 8 and (+)- 9 , which could be separated, thus making structure elucidation possible. The 6β-hydroxystigmasta-4,24(25)-dien-3-one ((+)- 4 ), also present in trace amounts in the sponge, was obtained in sufficient amount for NMR study, together with its C(6) epimer (+)- 11 , by hydroperoxidation of (+)- 8 followed by deoxygenation (Scheme 2). The last trace steroid of the sponge, stigmasta-4,6,24(25)-trien-3-one ((?)- 2 ), was structurally elucidated using limited NMR data and comparison with the other stigmastanes. These stigmastanes, as the only steroids of this sponge, are likely to function as stabilizers of its cell walls; their phytosteroid structure, for a sponge which lives in the dark of deep waters, suggest origin through a complex food chain, possibly followed by bioelaboration in the sponge.     

Reactivity-based One-pot Synthesis of Immunosuppressive Glycolipids from the Caribbean Sponge Plakortis simplex

The first synthesis of three natural glycolipid simplexides 1a – 1c , which were isolated from the marine sponge Plakortis simplex and claimed to inhibit T cell proliferation, has been concisely accomplished by a reactivity‐based one‐pot synthetic strategy under the use of p‐toluenethioglycoside (STol) donors.     

Callyptide A,a new cytotoxic peptide from the Red Sea marine sponge Callyspongia species

In the course of our continuing efforts to allocate bioactive secondary metabolites from Red Sea marine invertebrates, we have investigated the sponge Callyspongia species. The cytotoxic dichloromethane fraction of the methanolic extract of the sponge afforded a new cytotoxic peptide named callyptide A (1). Its structure was determined by extensive 1D and 2D NMR (COSY, HSQC and HMBC) studies and high-resolution mass spectral determination. The configuration of the amino acids was determined by Marfey’s analysis. Callyptide A was found to exhibit growth inhibitory activity when tested against different cancer cell lines.     

Rogiolol Acetate: A Novel β-Chamigrene-Type Sesquiterpene Isolated from a Marine Sponge

The marine sponge Spongia zimocca SCHMIDT , 1862, collected in front of the torrent II Rogiolo, south of Livorno, contains the sesquiterpene rogiolol acetate (= (+)-(2R,3S,6R,8R,9R)-2,8-dibromo-9-chloro-1,1,9-trimethyl-5-methylidenespiro[5.5]undec-3-yl acetate; (+)- 3a ), which represents the first chamigrane isolated from a sponge. Although compounds of this class are common in red seaweeds of the genus Laurencia, and our sponge actually contains 9-bromochamigrene and a variety of other metabolites of nearby growing Laurencia sp., (+)- 3a is unique to our sponge.     

Dysideasterols A–E,Five New Uncommon Polyhydroxylated Steroids from the South China Sea Sponge Dysidea sp.

Five new uncommon polyhydroxylated steroids, dysideasterols A–E ( 1 – 5 ), were isolated from the South China Sea sponge Dysidea sp. Their structures were established by detailed analysis of spectral data and verified via single‐crystal X‐ray‐diffraction analysis of compound 1 . The absolute configuration of 1 was determined by the modified Mosher method.     

Lingshuine,an Unexpected Passerini Product from the Hainan Sponge Axinyssa variabilis

Lingshuine ( 1 ), a novel sesquiterpene amide, along with three known N‐containing compounds, 2 – 4 , have been isolated from the Hainan sponge Axinyssa variabilis. The structure of 1 was elucidated by detailed analysis of the spectroscopic data and by chemical methods. Lingshuine represents the first example of a Passerini product formed during the isolation process.     

Dibromotyrosine derivatives from the ethanol extract of the marine sponge Aplysina sp.: structures,transformations, and origin

Twenty nine 3,5-dibromotyrosine derivatives were isolated from the ethanol extract of the marine sponge Aplysina sp. (South China Sea) including the earlier unknown compounds, in particular, p-hydroxycyclohexadienone and p-hydroxycyclohexenone ketals. The isolated enones, dienones, and ketals can be transformation products of aeroplysinin-1 in the course of its reactions with water and alcohols.     

Imidazolone and Imidazolidinone Artifacts of a Pivotal Imidazolthione,Zyzzin, from the poecilosclerid sponge Zyzza massalis from the coral sea. The first thermochromic systems of marine origin

Dry acetone extracts of the freeze-dried, deep-red powder of the poecilosclerid sponge Zyzza massalis (DENDY ) from the Coral Sea gave the orange alkaloid zyzzin (= 4-(1H-indol-3-yl)-1,5-dihydro-5-thioxo-1H-imidazol-2-one 14 ), which underwent exchange of the 5-thioxo for the 5-oxo group during aqueous chromatographic workup, giving yellow 13 . Both 13 and 14 added hydroxylic solvents at C(4)=N giving colourless, racemic products, 3 and 8 , respectively, by incorporation of MeOH and 10 and 11 , respectively, by incorporation of H₂O. On warming 3 or 10 in DMSO, 13 was recovered, thus furnishing a novel thermochromic system. Optically active (+)- 12 , which may be viewed to derive from enzymatic reduction of 14 at C(4)=N followed by S→O exchange, was also isolated from this sponge, along with the linear amides 16 and 19 . Compound 3 proved to have antibacterial and antifungal activities.     

24-Isopropylcholesterol and 22-Dehydro-24-isopropylcholesterol,Novel Sterols from a Sponge

24-Isopropycholesterol ( 1 ) and 22-dehydro-24-isopropylcholesterol 2 have been isolated as the only sterols from an Australian sponge of the genus Pseudaxinyssa. Structures have been deduced from spectroscopic data.     

Cacospongione A,cacospongienone A,and cacospongienone B,new C21 difuran terpenoids from the marine sponge Cacospongiascalaris SCHMIDT of the Côte d' Azur

The sponge Cacospongia scalaris (family Thorectidae), collected at the Cap de Nice (Cǒte d'Azur), is shown to contain a series of truncated, linear C₂₁ difuran terpenoids comprising the known sponge products furospongin-1 ((+)- 1 ), furospongin-2 ( 2 ), and dihydrofurospongin-2 ((?)-(E)- 3 ), besides the new products cacospongione A ((?)- 4 ), cacospongienone A ((?)-(Z)- 6 ), and cacospongienone B ((?)-(E)- 6 ), whose absolute configurations have been assigned by chemical correlations with (+)- 1 . Possibly, one of the two cacospongienones is an artifact, as these two terpenoids interconvert on standing. This is the first finding of linear C₂₁ difuran terpenoids, which are typical of the Spongiidae, in a member of the family Thorectidae.     

New Access to Sesquiterpene Hydroquinones: Synthesis of (+)‐ent‐Chromazonarol

A facile access to optically active (+)‐ent‐chromazonarol ent‐1, isolated from the sponge Disidea pallescens, is reported from commercially available (+)‐manool 4.     

Fatty acids from the Okhotsk sea sponge <Emphasis Type="Italic">Forcepia uschakowi</Emphasis>

The fatty-acid (FA) composition of total lipids from the Okhotsk sea marine sponge Forcepia uschakowi was studied. A total of 56 acids were identified by GC and GC—MS. The principal saturated acids were 16∶0 and 18∶0. The main monoene acid was 15-Me-24∶1(14), which was observed for the first time in sponge lipids. Polyunsaturated acids represented of 64.1% of the total FA of F. uschakowi. Of these, the principal ones were non-methylene-separated acids 26∶2(5,9) and 26∶3(5,9,19), which are typical of sponges, and bromo-acid 6-Br-26∶2(5,9). __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 422–424, September–October, 2007.     

Minor and Trace Sterols in Marine Invertebrates. XII. Occurrence of 24 (R + S)-isopropenylcholesterol, 24 (R + S)-methylcholesta-5, 25-dien-3β-ol,and 24 (R + S)-methylcholesta-7, 25-dien-3β-ol in the caribbean sponge,Verongia cauliformis

In addition to the two new sterols verongulasterol 11 and 25-dehydroaplysterol 13 of Verongia cauliformis³), which were reported earlier [2] [3], the minor and trace sterols of this sponge include five new sterols listed in the title (with the exception of the known 24 S-methyl-cholesta-5, 25-dien-3β-ol (codisterol, 1b ). The isolation of the 24(R)-epimer of codisterol is of interest, as this compound is a possibly biosynthetic precursor for aplysterol 12 , 25-dehydroaplysterol 13 , and verongulasterol 11 (all 24R) which occur in the same sponge [2]. A partial synthesis from fucosterol ( 4 ) of 24 (R + S)-isopropenylcholesterol ( 9 ), and of 24-isopropylcholesterol ( 10 ) is described.     

Hyrtiosins A–E,Five New Scalarane Sesterterpenes from the South China Sea Sponge Hyrtios erecta

Five new scalarane sesterterpenes, hyrtiosins A–E ( 1 – 5 ), together with three previously reported sesterterpenes, 25‐dehydroxy‐12‐epi‐scalarin ( 6 ), 12‐epi‐scalarin ( 7 ) and heteronemin ( 9 ), were isolated from the South China Sea sponge Hyrtios erecta. Their structures were determined on the basis of extensive NMR studies and high‐resolution MS measurements.     

Structure elucidation of the new citharoxazole from the Mediterranean deep‐sea sponge Latrunculia (Biannulata) citharistae

Citharoxazole (1), a new batzelline derivative featuring a benzoxazole moiety, was isolated from the Mediterranean deep‐sea sponge Latrunculia (Biannulata) citharistae Vacelet, 1969, together with the known batzelline C ( 2 ). This is the first chemical study of a Mediterranean Latrunculia species and the benzoxazole moiety is unprecedented for this family of marine natural products. The structure was mainly elucidated by the interpretation of NMR spectra and especially HMBC correlations. Copyright © 2011 John Wiley & Sons, Ltd.     

Ophiobolin Sesterterpenoids and Pyrrolidine Alkaloids from the Sponge‐Derived Fungus Aspergillus ustus

Chemical examination of the fungus Aspergillus ustus isolated from the Mediterranean sponge Suberites domuncula yielded the five new ophiobolin‐type sesterterpenoids 1 – 5 and the two new pyrrolidine alkaloids 6 and 7 , together with the known compound aurantiamine and cerebroside D. The structures of the new compounds were unambiguously elucidated on the basis of extensive spectroscopic‐data analysis (1D‐ and 2D‐NMR, MS, and UV) and comparison with literature data. All compounds were evaluated for their cytotoxicity against murine lymphoma cell line L5178Y.