ASPULVINONES, A NEW CLASS OF NATURAL-PRODUCTS FROM ASPERGILLUS-TERREUS - REINVESTIGATION OF STRUCTURES BY X-RAY CRYSTALLOGRAPHIC AND SPECTROSCOPIC ANALYSIS

被引:12
作者
BEGLEY, MJ [1 ]
GEDGE, DR [1 ]
KNIGHT, DW [1 ]
PATTENDEN, G [1 ]
机构
[1] UNIV NOTTINGHAM,DEPT CHEM,NOTTINGHAM NG7 2RD,ENGLAND
来源
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 | 1979年 / 01期
关键词
D O I
10.1039/p19790000077
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The constitutions of unsymmetrically substituted aspulvinone pigments from Aspergillus terreus are re-examined by a combination of X-ray crystallographic and spectroscopic analysis. The crystal structure of aspulvinone (18a) is determined by X-ray diffraction from diffractometer data by direct methods. Crystals are triclinic, space group P1, with Z = 2 in a unit cell of dimensions: a = 9.546 ± 0.005, b = 11.019 ± 0.005, c = 13.437 ± 0.006 Å, α = 102.94 ± 0.05, β = 113.73 ± 0.05, γ = 91.39 ± 0.15°. The structure was refined by least squares to R 0.054 for 2 106 independent reflections. Comparative spectroscopic data establish constitutions (18b) and (18d) for the structurally related metabolites. The present data, combined with synthetic studies, have led to the revision of structures assigned to all 'unsymmetrically' substituted aspulvinones found in A. terreus. The biosynthesis of this new class of natural products is considered.
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页码:77 / 83
页数:7
相关论文
共 23 条
[1]  
BEGLEY MJ, 1976, TETRAHEDRON LETT, P131
[2]  
CLAISEN L, 1895, LIEBIGS ANN CHEM, V284, P245
[3]   CONSTITUENTS OF HIGHER FUNGI .14. 3',4',4-TRIHYDROXYPULVINONE, THELEPHORIC ACID, AND NOVEL PYRANDIONE AND FURANONE PIGMENTS FROM SUILLUS-GREVILLEI (KLOTSCH) SING [BOLETUS-ELEGANS (SCHUM PER FRIES)] [J].
EDWARDS, RL ;
GILL, M .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1973, (18) :1921-1929
[4]  
GERMAIN G, 1971, ACTA CRYSTALLOGR A, V27, P360
[5]   NEW METABOLITES OF ASPERGILLUS-TERREUS - 3-HYDROXY-2,5-BIS-(P-HYDROXY-PHENYL)PENTA-2,4-DIEN-4-OLIDE AND DERIVATIVES [J].
GOLDING, BT ;
RICKARDS, RW ;
VANEK, Z .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1975, (19) :1961-1963
[6]   SYNTHESIS OF FREELINGYNE - ACETYLENIC SESQUITERPENE FROM EREMOPHILA-FREELINGII [J].
KNIGHT, DW ;
PATTENDEN, G .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1975, (07) :641-644
[7]   4-PHOSPHORANYLIDENEBUTENOLIDE INTERMEDIATES IN SYNTHESIS OF 4-YLIDENEBUTENOLIDES AND 4-YLIDENETETRONIC ACIDS - SYNTHESIS OF ALKYLIDENEPHTHALIDE CONSTITUENTS OF CELERY ODOR AND MODELS FOR FREELINGYNE [J].
KNIGHT, DW ;
PATTENDEN, G .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1975, (07) :635-640
[8]   SYNTHETIC APPROACHES TOWARDS 4-YLIDENEBUTENOLIDES AND 4-YLIDENETETRONIC ACIDS - REGIOSELECTIVE NUCLEOPHILIC ADDITIONS TO UNSYMMETRICALLY SUBSTITUTED MALEIC ANHYDRIDES [J].
KNIGHT, DW ;
PATTENDEN, G .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1979, (01) :62-69
[9]  
KNIGHT DW, 1979, J CHEM SOC PERK T 1, V1, P77