New Structural Insights into Saraines A, B, and C, Macrocyclic Alkaloids from the Mediterranean Sponge Reniera (Haliclona) sarai

被引:20
作者
Defant, Andrea [1 ]
Mancini, Ines [1 ]
Raspor, Lucija [1 ,2 ]
Guella, Graziano [1 ]
Turk, Tom [2 ]
Sepcic, Kristina [2 ]
机构
[1] Univ Trento, Dipartimento Fis, Chim Bioorgan Lab, I-38123 Povo, Italy
[2] Univ Ljubljana, Biotech Fac, Dept Biol, Ljubljana 1111, Slovenia
关键词
Natural products; Alkaloids; Nucleophilic addition; Mass spectrometry; Density functional calculations; 3-ALKYLPYRIDINIUM POLYMERS; NUCLEOPHILIC-ADDITION; INHIBITORS; STEREOCHEMISTRY;
D O I
10.1002/ejoc.201100434
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The structural peculiarity of saraines A, B and C, wherein a zwitterionic-like form is present due to the coordination of a nitrogen atom to the C-2 aldehyde by a strong proximity effect, has been further extended by experimental and theoretical evidences. They include the detection of [2M + H](+) clusters in electrospray ionization mass spectrometry in the positive ion mode of a water/acetonitrile solution, whereas only signals corresponding to [M + H](+) ions are detectable after addition of trifluoroacetic acid to the same solution. The zwitterionic form can be trapped to give O-methyl derivatives only by reaction with a strong alkylating agent such as Meerwein's reagent. DFT calculations carried out on the core structural model suggest that the nucleophilic N-1 atom in the minimized conformation is at a suitable distance from the carbonyl group and also defines an approach angle in good agreement with the Burgi-Dunitz model. Antibacterial and hemolytic activities and inhibition of acetylcholinesterase (AChE) assays have been evaluated for saraines A-C in comparison to those of saraines 1-3 and isosaraine 1, all the metabolites isolated from the sponge Reniera (Haliclona) sarai collected in the Northern Adriatic sea.
引用
收藏
页码:3761 / 3767
页数:7
相关论文
共 31 条
[1]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[2]   Total synthesis of (-)-Sarain A [J].
Becker, Michael H. ;
Chua, Peter ;
Downham, Robert ;
Douglas, Christopher J. ;
Garg, Neil K. ;
Hiebert, Sheldon ;
Jaroch, Stefan ;
Matsuoka, Richard T. ;
Middleton, Joy A. ;
Ng, Fay W. ;
Overman, Larry E. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (39) :11987-12002
[3]   PORE FORMATION BY THE SEA-ANEMONE CYTOLYSIN EQUINATOXIN-II IN RED-BLOOD-CELLS AND MODEL LIPID-MEMBRANES [J].
BELMONTE, G ;
PEDERZOLLI, C ;
MACEK, P ;
MENESTRINA, G .
JOURNAL OF MEMBRANE BIOLOGY, 1993, 131 (01) :11-22
[4]   Evaluation of the antifouling properties of 3-alyklpyridine compounds [J].
Blihoghe, Daniela ;
Manzo, Emiliano ;
Villela, Alexandre ;
Cutignano, Adele ;
Picariello, Gianluca ;
Faimali, Marco ;
Fontana, Angelo .
BIOFOULING, 2011, 27 (01) :99-109
[5]   GEOMETRICAL REACTION COORDINATES .2. NUCLEOPHILIC ADDITION TO A CARBONYL GROUP [J].
BURGI, HB ;
DUNITZ, JD ;
SHEFTER, E .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (15) :5065-5067
[6]   STEREOCHEMISTRY OF REACTION PATHS AT CARBONYL CENTERS [J].
BURGI, HB ;
DUNITZ, JD ;
LEHN, JM ;
WIPFF, G .
TETRAHEDRON, 1974, 30 (12) :1563-1572
[7]   SELECTED BIOLOGICAL-ACTIVITIES OF SARAINES [J].
CAPRIOLI, V ;
CIMINO, G ;
DEGIULIO, A ;
MADAIO, A ;
SCOGNAMIGLIO, G ;
TRIVELLONE, E .
COMPARATIVE BIOCHEMISTRY AND PHYSIOLOGY B-BIOCHEMISTRY & MOLECULAR BIOLOGY, 1992, 103 (01) :293-296
[8]   STRUCTURAL STUDIES ON SARAINE-A [J].
CIMINO, G ;
SCOGNAMIGLIO, G ;
SPINELLA, A ;
TRIVELLONE, E .
JOURNAL OF NATURAL PRODUCTS, 1990, 53 (06) :1519-1525
[9]  
CIMINO G, 1986, B SOC CHIM BELG, V95, P783
[10]  
CIMINO G, 1986, PURE APPL CHEM, V58, P375, DOI 10.1351/pac198658030375