Aranotin and related metabolites from Arachniotus aureus. I. Determination of structure

Ramakrishnan, Nagarajan; Huckstep, L. L.; Lively, David H.; DeLong, Donald C.; Marsh, Max M.; Neuss, Norbert

doi:10.1021/ja01013a055

Cited by 107 publications

(37 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…5) A known diketopiperazine, bisdethiodi(methylthio)-acetylaranotin (8), [6][7][8] was also isolated as an antimycobacterial constituent of the culture extract. We report herein the structure elucidation of the new compounds and biological activities of isolated compounds.…”

Section: Notementioning

confidence: 99%

Butyrolactones from the Fungus Aspergillus terreus BCC 4651

et al. 2010

View full text Add to dashboard Cite

NoteAs part of our research program on the utilization of bioresouces in Thailand, we have been screening fungal extracts for in vitro assays inclusive of antimycobacterial and antiplasmodial activities. An extract from Aspergillus terreus BCC 4651 exhibited moderate activity against Mycobacterium tuberculosis H37Ra (minimum inhibitory concentration (MIC) 25 mg/ml) and the 1 H-NMR spectrum of the extract showed a unique profile, therefore, we selected the strain for large scale fermentation and chemical investigation. This study led to the isolation of two new butenolides, butyrolactones VI (1) and VII (2), together with the known compounds, butylolactone I (3), 1) butyrolactone II (4), 2) butyrolactone IV (5),3) butyrolactone V (6), 4) and aspernolide B (7). 5) A known diketopiperazine, bisdethiodi(methylthio)-acetylaranotin (8), [6][7][8] was also isolated as an antimycobacterial constituent of the culture extract. We report herein the structure elucidation of the new compounds and biological activities of isolated compounds. Results and DiscussionInitial study of the cultures grown in a common liquid medium, Czapek-Dox broth, under shaking resulted in the isolation of the known compounds 3-5, 7, and 8. Further studies revealed that butyrolactone derivatives were efficiently produced when the fungus BCC 4651 was fermented in yeast extract sucrose medium (YES; a sucrose-rich liquid medium) under static conditions. The culture provided with two new compounds 1 and 2 along with 3, 5, 6 and terrein, which is one of the commonly occurring Aspergillus toxins. 9)These compounds were isolated by column chromatography (Sephadex LH-20, silica gel, and reversed-phase HPLC), wherein fractions were analyzed by TLC and 1 H-NMR. Compounds 3-5, and 7 were identified on the basis of the MS and NMR data as butyrolactone I, 1,3) butyrolactone II, 12) Methylation of 6 (MeI, K 2 CO 3 , N,N-dimethylformamide (DMF)) gave the dimethylated derivative 9, which was subsequently converted to the (S)-and (R)-a-methoxy-a-(trifluoromethyl)phenylacetic acid (MTPA) ester derivatives 10a and 10b, respectively. The Dd-values (d S -d R ) of the Mosher esters unambiguously indicated the 8ЉS-configuration (Fig. 1).Butyrolactone VI (1) was isolated as a colorless solid. The molecular formula was determined to be C 24 H 26 O 9 by high resolution-electrospray ionization-mass spectra (HR-ESI-MS). The IR spectrum showed broad and intense absorption bands at n max 3442 (broad) and 1739 cm Ϫ1. The 1 H-and 13 C-NMR spectra were similar to those of other butyrolactone Butyrolactones from the Fungus Aspergillus terreus BCC 4651Rachada HARITAKUN, Pranee RACHTAWEE, Rungtiwa CHANTHAKET, Nattawut BOONYUEN, and Masahiko ISAKA* National Center for Genetic Engineering and Biotechnology; 113 Thailand Science Park, Phaholyothin Road, Klong Luang, Pathumthani 12120, Thailand. Received July 16, 2010; accepted August 3, 2010; published online August 6, 2010 Two new butenolides, butyrolactones VI (1) and VII (2), were isolated together with six known compounds, but...

show abstract

Section: Notementioning

confidence: 99%

Butyrolactones from the Fungus Aspergillus terreus BCC 4651

et al. 2010

View full text Add to dashboard Cite

show abstract

“…The CS-SC moiety occurs in antibiotics such as gliotoxin, sporidesmin, and acetylaranotin in the form of an S-S bridged piperazinedione system in which the CS-SC dihedral angle is severely restricted by ring closure (1,2). Hormones, such as oxytocin (3), vasopressin (4), and malformin (5), contain disulfide bonds (cystine) that can assume conformations with widely varying dihedral angle, depending upon ring size and other structural constraints.…”

mentioning

confidence: 99%

Disulfide Bond Dihedral Angles from Raman Spectroscopy

Wart

Lewis

Scheraga

et al. 1973

Proc. Natl. Acad. Sci. U.S.A.

169

103

View full text Add to dashboard Cite

Raman spectra of several compounds containing the CS-SC moiety were obtained (in the solid phase) from 450-800 cm-' to investigate the S-S and C-S stretching behavior. The S-S stretching frequency varied linearly with the CS-SC dihedral angle (obtained from either x-ray or neutron diffraction or ultraviolet absorption) for compounds whose CC-SS dihedral angles were not very different. The ratio of the intensities of the S-S and C-S stretching bands exhibited no recognizable correlation with either the CS-SC dihedral angle or the CSS bond angle, probably because this ratio is sesisitive to the crystalline environment. The linear dependence of the S-S stretching frequency on dihedral angle leads to a dihedral angle for the plant hormone, malformin A, that is in excellent agreement with that estimated from the longest wavelength CS-SC ultraviolet absorption band.The disulfide bond is an important structural feature of many important biological molecules. The CS-SC moiety occurs in antibiotics such as gliotoxin, sporidesmin, and acetylaranotin in the form of an S-S bridged piperazinedione system in which the CS-SC dihedral angle is severely restricted by ring closure (1, 2). Hormones, such as oxytocin (3), vasopressin (4), and malformin (5), contain disulfide bonds (cystine) that can assume conformations with widely varying dihedral angle, depending upon ring size and other structural constraints. In globular proteins, such as ribonuclease, chymotrypsin, lysozyme, carboxypeptidase, etc., packing requirements may result in dihedral angles that vary substantially from the widely accepted value (6) of about 900 for L-cystine in aqueous solution. In chymotrypsin, for example, this angle varies from 87°-126°(7). It is, therefore, of considerable importance to have a method that can provide information about this dihedral angle both in solid state and in aqueous solution. Raman spectroscopy appears to be a suitable technique for this purpose, since the Raman spectra of compounds containing disulfide bonds usually show welldefined bands that arise from C-S and S-S stretching modes (8,9), and these vibrations might be sensitive to the CS-SC dihedral angle.Absorption spectra can also be used to obtain information about CS-SC dihedral angles, since the relationship between this dihedral angle and the longest-wavelength CS-SC absorption frequency in the ultraviolet is well established both theoretically (10) and experimentally (see references cited in ref. 10). However, this method for determining CS-SC dihedral angles is limited to simple systems in which the UV absorption spectrum is free from nondisulfide-related transitions from about 250 to 380 nm. Many systems (proteins for example, which contain aromatic residues) have nondisulfide chromophores that absorb in this region, and thus prevent study of the CS-SC absorption bands. On the other hand, as t To whom requests for reprints should be addressed. 2619has been pointed out (8, 9), these compounds (including proteins) exhibit S-S and C-S stretching bands in a reg...

show abstract

“…Through repeated silica gel chromatography, Sephadex LH-20 and preparative HPLC, the EtOAc extract of the fermentation broth of A. terreus MHL-P22 afforded two new furandione derivatives, asperterone B (1) and C (2), along with four known metabolites, bisdethiodi(methylthio)-acetylaranotin (3), 10) The authors declare no conflict of interest.…”

Section: Resultsmentioning

confidence: 99%

Furandiones from an Endophytic <i>Aspergillus terreus</i> Residing in <i>Malus halliana</i>

Qiao

2012

Chem. Pharm. Bull.

View full text Add to dashboard Cite

Two new furandiones named asperterone B (1) and C (2) together with four known metabolites (3-6) were isolated from the liquid culture of the endophytic fungus Aspergillus terreus MHL-P22 residing in the fresh leaves of Malus halliana. The structures of the new compounds were elucidated by analysis of their MS, IR, 1D-and 2D-NMR spectra. 1 and 2 showed moderate cytotoxic activities against human colorectal carcinoma SW1116 cells with IC 50 values of 57.5 and 71.0 µM, respectively. The biosynthetic pathway for 1, 2 and their analogues was also postulated and briefly discussed.

show abstract

Aranotin and related metabolites from Arachniotus aureus. I. Determination of structure

Cited by 107 publications

References 1 publication

Butyrolactones from the Fungus Aspergillus terreus BCC 4651

Butyrolactones from the Fungus Aspergillus terreus BCC 4651

Disulfide Bond Dihedral Angles from Raman Spectroscopy

Furandiones from an Endophytic <i>Aspergillus terreus</i> Residing in <i>Malus halliana</i>

Contact Info

Product

Resources

About