Sesquiterpene thiocyanates and isothiocyanates from Axinyssa aplysinoides

He, Hai Yin; Salvá, Javier; Catalos, Robert F.; Faulkner, D. John

doi:10.1021/jo00037a042

Cited by 58 publications

(49 citation statements)

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“…; [27,28] the C9 epimer of 9-isocyanopupukeanane from the nudibranch P. bourguini; [29] 2-thiocyanatopupukeanane from a Palauan sponge of Axinyssa aplysinoides; [30] 9-isothiocyanatopupukeanane from the sponge Axinyssa sp. [31] Some neopupukeananes have also been isolated from marine sponges, such as 2-and 4-thiocyanatoneopupukeanane [30,32] and 9-isocyanoneopupukeanane. [33] Prior to the discovery of chloropupukeananin (1), [15] chloropupukeanolides A (5) and B (6), [19] and chloropupukeanone A (7), [19] the only example with a tricyclo-[4.3.1.0 3,7 ]-decane carbon skeleton from terrestrial sources was nemorosonol, a polyisoprenylated pupukeanane from the fruits of the South-American plant Clusia nemorosa and the leaves of the Vietnamese plant Garcinia bracteata (both of the Clusiaceae family).…”

Section: Discussionmentioning

confidence: 99%

Chloropupukeanolides C–E: Cytotoxic Pupukeanane Chlorides with a Spiroketal Skeleton from Pestalotiopsis fici

Liu

Bruhn

Guo

et al. 2011

Chemistry A European J

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Chloropupukeanolides C-E (8-10), three highly functionalized secondary metabolites featuring a novel spiroketal skeleton derived from the chlorinated tricyclo-[4.3.1.0(3, 7)]-decane (pupukeanane) and the 2,6-dihydroxy-4-methylbenzoic acid moieties, were isolated from the scale-up fermentation extract of the plant endophytic fungus Pestalotiopsis fici. The constitutions of compounds 8-10 were elucidated primarily by NMR experiments. Their relative configurations were deduced by analogy to metabolites 4-6, which were previously isolated from the same fungus. The absolute configuration of 8 was assigned by X-ray crystallography and those of 9 and 10 by quantum-chemical CD calculations. Biogenetically, chloropupukeanolides C-E (8-10) are presumably derived from the same oxidation-induced Diels-Alder reaction pathway as compounds 1 and 4-7, via the putative biosynthetic precursors 2 and 3. The opposite configurations of the complete "Southern parts" of 8 and 9 suggests that this Diels-Alder reaction is stereochemically not very selective. Compounds 8-10 showed significant cytotoxicity against a small panel of human tumor cell lines and weak activities against the pathogens of tropical diseases.

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Section: Discussionmentioning

confidence: 99%

Chloropupukeanolides C–E: Cytotoxic Pupukeanane Chlorides with a Spiroketal Skeleton from Pestalotiopsis fici

Liu

Bruhn

Guo

et al. 2011

Chemistry A European J

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“…109 Subsequent studies of A. aplysinoides uncovered another thiocyanate 147, 110 an isonitrile 148, a formamide 149, a tyrosine derivative 150, two unrelated diterpenes, neoverrucosan-5β-ol and homoverrucosan-5β-ol 111 and the formamide 151 and urea 152, 112 with the structures of 141 and 151 being determined by X-ray analysis. Although sesquiterpene isonitriles, formamides and isothiocyanates are believed to be feeding deterrents, no such studies with this particular group of compounds have been reported.…”

Section: Axinyssa Aplysinoides ‫؍(‬ Trachyopsis Aplysinoides)mentioning

confidence: 99%

Investigations of the Marine Flora and Fauna of the Islands of Palau

Faulkner¹,

Newman²,

Cragg³

2004

ChemInform

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“…1) Previous chemical investigations on sponges of the genus Axinyssa (order Halichondrida, family Halichondriidae) have led to the isolation and identification of various sesquiterpenes containing unusual nitrogenous functional groups as an isocyano, isothiocyanate, thiocyanate, bisabolene and formamide group. [2][3][4][5][6][7][8][9][10][11][12][13][14][15] Some of these N-containing compounds have been found to possess several kinds of biological activities, such as antithelmintic, 2) antimicrobial, 4) antimalarial, 6) antifouling, 11) cytotoxic activities 12) and lethality for brine shrimp. 10) Our investigation of the chemical constituents of a sponge Axinyssa sp.…”

mentioning

confidence: 99%

New Nitrogenous Bisabolene-Type Sesquiterpenes from a Formosan Sponge <i>Axinyssa</i> sp.

Liu

Liang

Chiang

et al. 2014

CHEMICAL & PHARMACEUTICAL BULLETIN

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Key words sponge; Axinyssa sp.; bisabolene-type; cytotoxicity Studies in the chemistry of marine natural products, the marine sponges have emerged as one of the most prolific sources for discovery of novel secondary metabolites.1) Previous chemical investigations on sponges of the genus Axinyssa (order Halichondrida, family Halichondriidae) have led to the isolation and identification of various sesquiterpenes containing unusual nitrogenous functional groups as an isocyano, isothiocyanate, thiocyanate, bisabolene and formamide group.2-15) Some of these N-containing compounds have been found to possess several kinds of biological activities, such as antithelmintic, 2) antimicrobial, 4) antimalarial, 6) antifouling, 11) cytotoxic activities 12) and lethality for brine shrimp. 10) Our investigation of the chemical constituents of a sponge Axinyssa sp. yielded two new nitrogenous bisabolene-type sesquiterpenes, axinysalines A (1) and B (2), along with three known sesquiterpenes. The structures of 1 and 2 were established by detailed spectroscopic analysis and comparison of their NMR data with those of known analogues. The known sesquiterpenes were readily identified as 3-isocyanotheonellin (3), 16) 3-isocyano-7,8-epoxy-α-bisabolane (4) 7) and 3-formamidotheonellin (5), 17) by comparison of their spectral data with those reported in the literature. The cytotoxicity of metabolites 1-5 against the six cancer cell lines, human erythromyeloblastoid leukemia (K562), human T lymphoblast, acute lymphoblastic leukemia (Molt 4), human colon adenocarcinoma (HCT-116 and DLD-1), and human breast carcinoma (MDA-MB-231 and T47D) was studied.Compound 1, named axinysaline A, was isolated as an optically active, colorless oil. The molecular formula was determined to be C 21 H 35 NO 3 by high resolution-electrospray ionization (HR-ESI)-MS (m/z 372.2515, C 21 H 35 NO 3 Na) and NMR data, which corresponded to five degrees of unsaturation. The IR spectrum of 1 showed absorption bands at 3375, 1679 and 1746 cm −1 , suggesting the presence of an amide CO group and an ester CO group, which were supported by 13 C-NMR chemical shifts at δ 171.9 and 169.2 ppm, respectively. The 13 C-NMR and distortionless enhancement by polarization transfer (DEPT) spectral data of 1 showed the presence of 21 carbons (Table 1): seven methyls, four sp 3 methylenes, two sp 3 methines, three sp 2 methines, and two sp 3 quaternary carbons. The remaining three signals appearing in the lower field region of the spectrum are due to the quaternary carbons of one olefinic carbon (δ 140.2), one amide carbonyl and one ester carbonyl. From the 1 H-NMR spectrum of 1, the resonances of three olefinic protons (δ H 6.22, dd, J=14.5, 11.0 Hz; 5.81, d, J=11.0 Hz; 5.59 dd, J=15.5,7.0 Hz) were observed. Moreover, analysis of the 1

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Sesquiterpene thiocyanates and isothiocyanates from Axinyssa aplysinoides

Cited by 58 publications

References 0 publications

Chloropupukeanolides C–E: Cytotoxic Pupukeanane Chlorides with a Spiroketal Skeleton from Pestalotiopsis fici

Chloropupukeanolides C–E: Cytotoxic Pupukeanane Chlorides with a Spiroketal Skeleton from Pestalotiopsis fici

Investigations of the Marine Flora and Fauna of the Islands of Palau

New Nitrogenous Bisabolene-Type Sesquiterpenes from a Formosan Sponge <i>Axinyssa</i> sp.

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