Wijeratne E M Kithsiri, Turbyville Thomas J, Zhang Zhongge, Bigelow Donna, Pierson Leland S, VanEtten Hans D, Whitesell Luke, Canfield Louise M, Gunatilaka A A Leslie
SW Center for Natural Products Research and Commercialization, Office of Arid Lands Studies, College of Agriculture and Life Sciences, University of Arizona, 250 E. Valencia Road, Tucson, Arizona 85706-6800, USA.
J Nat Prod. 2003 Dec;66(12):1567-73. doi: 10.1021/np030266u.
A novel cyclopentenedione, asterredione (1), two new terrecyclic acid A derivatives, (+)-5(6)-dihydro-6-methoxyterrecyclic acid A (2) and (+)-5(6)-dihydro-6-hydroxyterrecyclic acid A (3), and five known compounds, (+)-terrecyclic acid A (4), (-)-quadrone (5), betulinan A (6), asterriquinone D (7), and asterriquinone C-1 (8), were isolated from Aspergillus terreus occurring in the rhizosphere of Opuntia versicolor, using bioassay-guided fractionation. Acid-catalyzed reaction of 2 under mild conditions afforded 4, whereas under harsh conditions 2 yielded 5 and (-)-isoquadrone (9). Catalytic hydrogenation and methylation of 4 afforded 5(6)-dihydro-terrecyclic acid A (10) and (+)-terrecyclic acid A methyl ester (11), respectively. The structures of 1-11 were elucidated by spectroscopic methods. All compounds were evaluated for cytotoxicity in a panel of three sentinel cancer cell lines, NCI-H460 (non-small cell lung cancer), MCF-7 (breast cancer), and SF-268 (CNS glioma), and were found to be moderately active. Cell cycle analysis of 2, 4, and 5 using the NCI-H460 cell line indicated that 4 is capable of disrupting the cell cycle through an apparent arrest to progression at the G(1) and G(2)/M phases in this p53 competent cell line. A pathway for the biosynthetic origin of asterredione (1) from asterriquinone D (7) is proposed.
采用生物活性追踪分离法,从生长于变色仙人掌根际的土曲霉中分离得到一种新型环戊二酮——紫星二酮(1)、两种新的四环酸A衍生物,即(+)-5(6)-二氢-6-甲氧基四环酸A(2)和(+)-5(6)-二氢-6-羟基四环酸A(3),以及5种已知化合物(+)-四环酸A(4)、(-)-醌型化合物(5)、桦木南A(6)、紫星醌D(7)和紫星醌C-1(8)。在温和条件下,2经酸催化反应生成4;而在苛刻条件下,2生成5和(-)-异醌型化合物(9)。4经催化氢化和甲基化反应,分别得到5(6)-二氢四环酸A(10)和(+)-四环酸A甲酯(11)。通过光谱方法确定了1-11的结构。对所有化合物在三种指示癌细胞系NCI-H460(非小细胞肺癌)、MCF-7(乳腺癌)和SF-268(中枢神经系统胶质瘤)中进行了细胞毒性评估,发现它们具有中等活性。使用NCI-H460细胞系对2、4和5进行细胞周期分析表明,在这个p53功能正常的细胞系中,4能够通过明显阻滞G(1)期和G(2)/M期的进程来扰乱细胞周期。提出了一条从紫星醌D(7)生物合成紫星二酮(1)的途径。