Isolation, structure elucidation, and biomimetic total synthesis of versicolamide B, and the isolation of antipodal (-)-stephacidin A and (+)-notoamide B from Aspergillus versicolor NRRL 35600
Isolation, structure elucidation, and biomimetic total synthesis of versicolamide B, and the isolation of antipodal (-)-stephacidin A and (+)-notoamide B from Aspergillus versicolor NRRL 35600
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DOI：
10.1002/anie.200800106
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发表时间：
2008-01-01
影响因子：
16.6
通讯作者：
Williams, Robert M.
中科院分区：
文献类型：
--
作者：
Greshock, Thomas J.;Grubbs, Alan W.;Williams, Robert M.
含双环-[2.2]的戊基化吲哚类生物碱。2]重氮辛烷环系为核心结构，目前家族成员数超过38个。这些天然物质，由不同属的真菌，特别是曲霉和青霉菌（以及其他）产生，表现出一系列有趣的结构和立体化学特征。值得注意的是，这个家族的成员显示出无数的生物活性，包括杀虫、抗肿瘤、驱虫药、抑制钙调素和抗菌特性。从结构上讲，这些物质是由一个或两个异戊二烯单位、色氨酸和另一种环氨基酸残基如脯氨酸、β-甲基脯氨酸或胡椒酸的氧化缩合而产生的。相对立体化学在核心双环内[2.2]。[2]在重氮辛烷环体系中，所有已知的对苯二甲酰胺家族成员，如对苯二甲酰胺（1和2）、stephacidins（3和4）和notoamide（5和6）都具有同步构型，而只有短甲酰胺（9和10）具有反相对构型（方案1）。顺/反关系是指环氨基酸残基（脯氨酸、β-甲基脯氨酸或胡椒酸；方案2）的C19ÀC22键（核硫酰胺编号）与C17ÀN13键之间的相对构型。这一关系揭示了为了在氧化环化过程中生物合成构建核心环体系，异戊二烯衍生的亲二烯试剂的两个面都参与了环的形成过程。然而,
Prenylated indole alkaloids containing the bicyclo-[2.2. 2] diazaoctane ring system as a core structure, now number more than 38 family members. These natural substances, produced by various genera of fungi, in particular Aspergillus and Penicillium spp.(among others), exhibit a range of interesting structural and stereochemical features. Significantly, a myriad of biological activities, including insecticidal, antitumor, anthelmintic, calmodulin inhibitory, and antibacterial properties, are displayed by members of this family. Structurally, these substances arise from the oxidative condensation of one or two isoprene units, tryptophan, and another cyclic amino acid residue such as proline, β-methylproline, or pipecolic acid. With respect to the relative stereochemistry within the core bicyclo [2.2. 2] diazaoctane ring system, all of the known members of the paraherquamide family, for example, paraherquamides (1 and 2), stephacidins (3 and 4), and notoamides (5 and 6) possess a syn configuration, while only the brevianamides (9 and 10) possess the anti relative configuration (Scheme 1). The syn/anti relationship refers to the relative configuration between the C19ÀC22 bond (sclerotiamide numbering) and the C17ÀN13 bond of the cyclic amino acid residue (proline, β-methylproline, or pipecolic acid; Scheme 2). This relationship reveals that to construct the core ring system biosynthetically in the oxidative cyclization process (es) both faces of the isoprene-derived dienophile participate in the ring-forming process. However,