NOVEL MARINE POLYHYDROXYLATED STEROIDS FROM THE STARFISH MYXODERMA-PLATYACANTHUM

被引：77

作者：

FINAMORE, E ^{[1
]}

MINALE, L ^{[1
]}

RICCIO, R ^{[1
]}

RINALDO, G ^{[1
]}

ZOLLO, F ^{[1
]}

机构：

[1] UNIV NAPOLI FEDERICO 2,DIPARTIMENTO CHIM SOSTANZE NAT,VIA DOMENICO MONTESANO 49,I-80131 NAPLES,ITALY

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 03期

关键词：

D O I：

10.1021/jo00003a043

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Nine polyhydroxy steroids and two steroid glycosides have been isolated from the starfish Myxoderma platyacanthum. The novel compounds 1-7 possess the same 3-beta, 5-alpha,6-beta,15-alpha-tetrol necleus (15-sulfated in 1 and 3) but differ in the side chains. Two levels of oxidation (CH2OH and CO2H) at the side chain methyls were encountered in this class of steroids; in 6 and 7 the 26-carboxylic acid function is found as amide derivative of taurine. The novel compound 8 is an asterosaponin assigned as myxodermoside A, consisting of a DELTA-9(11) 3-beta,6-alpha-dihydroxysteroidal moiety, a tetrasaccharide portion attached at C-6, and a sulfate group at C-3. Steroids 9-11 have known structures. The general structure of the novel compounds was determined from spectral data (H-1 and C-13 NMR and FAB MS), and the stereochemistry of the side chains was determined by correlating the respective spectral data with those of synthetic models of known configuration. The stereoselective synthesis of the steroid 4 side chain (DELTA-22E, 27-nor-24-methyl-26-carboxy) is also described.

引用

页码：1146 / 1153

页数：8

共 35 条

[1] CONFIGURATION ASSIGNMENT OF 24R-ISOMERS AND 24S-ISOMERS OF 29-OXYGENATED STEROIDS BY H-1 AND C-13 NMR-SPECTROSCOPY [J].

ANASTASIA, M ;

ALLEVI, P ;

CIUFFREDA, P ;

RICCIO, R .

TETRAHEDRON, 1986, 42 (17) :4843-4847

[2] MICROBIOLOGICAL HYDROXYLATION OF STEROIDS .1. PROTON MAGNETIC RESONANCE SPECTRA OF KETONES, ALCOHOLS, AND ACETATES IN ANDROSTANE, PREGNANE, AND CESTRANE SERIES [J].

BRIDGEMA.JE ;

CHERRY, PC ;

CLEGG, AS ;

EVANS, JM ;

JONES, ERH ;

KASAL, A ;

KUMAR, V ;

MEAKINS, GD ;

MORISAWA, Y ;

RICHARDS, EE ;

WOODGATE, PD .

JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC, 1970, (02) :250-&

[3]

BRUNO I, 1990, GAZZ CHIM ITAL, V120, P449

[4] STARFISH SAPONINS .14. STRUCTURES OF THE STEROIDAL GLYCOSIDE SULFATES FROM THE STARFISH MARTHASTERIAS-GLACIALIS [J].

BRUNO, I ;

MINALE, L ;

PIZZA, C ;

ZOLLO, F ;

RICCIO, R ;

MELLON, FM .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1984, (08) :1875-1883

[5] ALPHA-METHOXY-ALPHA-TRIFLUOROMETHYLPHENYLACETIC ACID, A VERSATILE REAGENT FOR DETERMINATION OF ENANTIOMERIC COMPOSITION OF ALCOHOLS AND AMINES [J].

DALE, JA ;

DULL, DL ;

MOSHER, HS .

JOURNAL OF ORGANIC CHEMISTRY, 1969, 34 (09) :2543-&

[6] NUCLEAR MAGNETIC-RESONANCE ENANTIOMER REAGENTS - CONFIGURATIONAL CORRELATIONS VIA NUCLEAR MAGNETIC-RESONANCE CHEMICAL-SHIFTS OF DIASTEREOMERIC MANDELATE, O-METHYLMANDELATE, AND ALPHA-METHOXY-ALPHA-TRIFLUOROMETHYLPHENYLACETATE (MTPA) ESTERS [J].

DALE, JA ;

MOSHER, HS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (02) :512-519

[7]

DAURIA MV, 1984, GAZZ CHIM ITAL, V114, P469

[8]

DAURIA MV, 1990, GAZZ CHIM ITAL, V120, P155

[9]

DAURIA MV, IN PRESS J CHEM S P1

[10]

DUBOIS MA, 1988, LIEBIGS ANN CHEM, P845

← 1 2 3 4 →