- General Fmoc-Based Solid-Phase Synthesis of Complex Depsipeptides Circumventing Problematic Fmoc Removal
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Development of an Fmoc-based solid-phase depsipeptide methodology has been hampered by base-promoted fragmentation and diketoperazine formation upon Fmoc group elimination. Such a strategy would be a useful tool given the number of commercially available Fmoc-protected residues. Herein we report that the addition of small percentages of organic acids to the Fmoc-removal cocktail proves effective to circumvent these drawbacks and most importantly, allowed the development of an exclusively solid-phase stepwise methodology to prepare a highly complex depsipeptide with multiple and consecutive esters bonds. Alongside, the optimal protecting group scheme for residue incorporation, which is not as straightforward as it is for traditional peptide synthesis, was explored. The developed stepwise strategy proved effective for the synthesis of a highly complex cyclodepsipeptide, being comparable to the yields obtained when using traditional combined chemistry approaches.
- Lobo-Ruiz, Ariadna,Tulla-Puche, Judit
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supporting information
p. 183 - 192
(2020/01/24)
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- Minutissamides E-L, antiproliferative cyclic lipodecapeptides from the cultured freshwater cyanobacterium cf. Anabaena sp.
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The extract of UIC 10035, a strain obtained from a sample collected near the town of Homestead, South Florida, showed antiproliferative activity against MDA-MB-435 cells. Bioassay-guided fractionation led to the isolation of a series of cyclic lipodecapeptides, named minutissamides E-L (1-8). The planar structures were determined by analysis of HRESIMS, tandem MS, and 1D and 2D NMR data, and the stereoconfigurations were assigned by LC-MS analysis of the Marfey's derivatives after acid hydrolysis. Minutissamides E-L (1-8) exhibited antiproliferative activity against MDA-MB-435 cells with IC50 values ranging between 1 and 10 μM. The structures of minutissamides E-L (1-8) were closely related with those of the previously reported lipopeptides, puwainaphycins A-E and minutissamides A-D, characterized by the presence of a lipophilic β-amino acid and three non-standard amino acids NMeAsn, OMeThr and Dhb (α,β-dehydro-α-aminobutyric acid). The strain UIC 10035 was designated as cf. Anabaena sp. on the basis of morphological and 16S rRNA gene sequence analyses.
- Kang, Hahk-Soo,Sturdy, Megan,Krunic, Aleksej,Kim, Hyunjung,Shen, Qi,Swanson, Steven M.,Orjala, Jimmy
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supporting information
p. 6134 - 6143
(2012/11/07)
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- Perthamides C and D, two new potent anti-inflammatory cyclopeptides from a Solomon Lithistid sponge Theonella swinhoei
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Two new metabolites, perthamides C and D, have been isolated from the marine sponge Theonella swinhoei. Their structures were determined by interpretation of NMR and ESIMS data. All compounds exhibited in vivo potent anti-inflammatory activity. Biological
- Festa, Carmen,De Marino, Simona,Sepe, Valentina,Monti, Maria Chiara,Luciano, Paolo,D'Auria, Maria Valeria,Débitus, Cecile,Bucci, Mariarosaria,Vellecco, Valentina,Zampella, Angela
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experimental part
p. 10424 - 10429
(2010/03/04)
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- Homophymine A, an anti-HIV cyclodepsipeptide from the sponge Homophymia sp.
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(Chemical Equation Presented) A new anti-HIV cyclodepsipeptide, homophymine A, was isolated from a New Caledonian collection of the marine sponge Homophymia sp. The structure of homophymine A was determined by interpretation of spectroscopic data, acid hydrolysis, and LC-MS analysis. Homophymine A contains 11 amino acid residues and an amide-linked 3-hydroxy-2,4,6- trimethyloctanoic acid moiety. Along with four D-, two L-, and one N-methyl amino acids, it also contains four unusual amino acid residues: (2S,3S,4R)-3,4-diMe-Gln, (2R,3R,4S)-4-amino-2,3-dihydroxy-1,7-heptandioic acid, L-ThrOMe, and (2R,3R,4R)-2-amino-3-hydroxy-4,5-dimethylhexanoic acid. In a cell-based XTT assay, homophymine A exhibited cytoprotective activity against HIV-1 infection with a IC50 of 75 nM.
- Zampella, Angela,Sepe, Valentina,Luciano, Paolo,Bellotta, Filomena,Monti, Maria Chiara,D'Auria, Maria Valeria,Jepsen, Trine,Petek, Sylvain,Adeline, Marie-Therese,Laprevote, Olivier,Aubertin, Anne-Marie,Debitus, Cecile,Poupat, Christiane,Ahond, Alain
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p. 5319 - 5327
(2008/12/22)
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- Novel jadomycins: Incorporation of non-natural and natural amino acids
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Electrospray ionization mass spectrometry of extracts from Streptomyces venezuelae ISP5230 cultures grown on chemically synthesized non-natural l-amino acids, d-amino acids or any of the 20 natural amino acids demonstrated incorporation of the amino acid into a jadomycin B analogue.
- Jakeman, David L.,Farrell, Spring,Young, Wendy,Doucet, Rene J.,Timmons, Shannon C.
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p. 1447 - 1449
(2007/10/03)
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