thaxtomin A | 122380-18-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: thaxtomin A
• 英文别名: (3R,6S)-3-hydroxy-3-[(3-hydroxyphenyl)methyl]-1,4-dimethyl-6-[(4-nitro-1H-indol-3-yl)methyl]piperazine-2,5-dione
• CAS: 122380-18-1
• 化学式: C₂₂H₂₂N₄O₆
• 分子量: 438.44
• InChiKey: QRDNJYNIEGRRKV-PGRDOPGGSA-N

物化性质

• 溶解度：
  DMF：可溶； DMSO：可溶；乙醇：部分溶解；甲醇：部分溶解

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  143
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  D-葡萄糖 、 thaxtomin A 在 bacillus mycoides isolate (HL-BM-1) 、 oatmeal medium 、 zinc(II) sulfate 作用下， 以 水 为溶剂， 反应 96.0h， 生成 thaxtomin A β-D-glucoside
  参考文献：
  名称：

  Microbial Glucosylation of Thaxtomin A, a Partial Detoxification

  摘要：

  Thaxtomin A (1) and B (2), the two major phytotoxins associated with the common scab of potato disease, were transformed into C-14 linked beta-glucosides (3) and (4), respectively, when individually incubated with cultures of Bacillus mycoides in oatmeal broth at 26 degrees C. These biotransformation products when assayed on aseptically produced potato minitubers proved to be much less phytotoxic than the parent compounds.

  DOI：

  10.1021/jf990912o
• 作为产物：
  描述：

  iso-thaxtomin A 在 三乙胺 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以165 mg的产率得到thaxtomin A
  参考文献：
  名称：

  Thaxtomin A及其立体异构体的合成方法

  摘要：

  本发明涉及Thaxtomin A及其立体异构体的合成方法，它们的化学结构为：本发明还提供了其合成方法，该合成路线的特点为高效，异构体的拆分可通过重结晶获得，有利于目标产物的大量制备。

  公开号：

  CN104557878B

文献信息

• [EN] METHODS AND COMPOSITIONS FOR SUBSTITUTED 2,5-DIKETOPIPERAZINE ANALOGS<br/>[FR] PROCÉDÉS ET COMPOSITIONS POUR DES ANALOGUES DE 2,5-DICÉTOPIPÉRAZINES SUBSTITUÉES
  申请人：UNIV FLORIDA

  公开号：WO2019222552A1

  公开（公告）日：2019-11-21

  Thaxtomins are phytotoxic secondary metabolites produced in plant pathogenic Streptomyces strains and have received considerable interests as bioherbicides. A cell-free, biocombinatorial approach was developed to produce a thaxtomin library for herbicide development. Combination of biosynthetic enzymes led to the production of 136 substituted 2,5-diketopiperazines, thaxtomin D, thaxtomin B and thaxtomin A analogs in a single pot. Furthermore, rational engineering of TxtA allowed the synthesis of azido-containing thaxtomin analog. Selected unnatural thaxtomins demonstrated improved herbicidal activities.This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.

  Thaxtomins是植物病原链霉菌产生的植物毒素性次生代谢产物，作为生物除草剂引起了相当大的兴趣。一种无细胞的生物组合方法被开发出来，用于生产一个thaxtomin草甘膦库以进行除草剂的开发。通过生物合成酶的组合，可以在一个容器中生产136种取代的2,5-二酮哌嗪，thaxtomin D，thaxtomin B和thaxtomin A类似物。此外，对TxtA的合理工程改造使得可以合成含有偶氮基的thaxtomin类似物。选择的非自然thaxtomins表现出改进的除草活性。本摘要旨在作为在特定领域中进行搜索的扫描工具，不限于目前的披露。
• Total Synthesis of Thaxtomin A and Its Stereoisomers and Findings of Their Biological Activities
  作者：Hongbo Zhang、Xin Ning、Hang Hang、Xuyan Ru、Haichen Li、Yonghong Li、Lizhong Wang、Xiao Zhang、Shujing Yu、Yuanyuan Qiao、Xin Wang、Peng George Wang

  DOI：10.1021/ol4026556

  日期：2013.11.15

  The first and facile total synthesis of thaxtomin A and its three stereoisomers has been achieved. The synthetic approach involves intramolecular nucleophilic cyclization of an amide toward a ketoamide group to produce a C-hydroxydiketopiperazine scaffold. The most amazing discovery was that each of the four stereoisomers of TA exhibits different phytotoxic, fungicidal, and antiviral activities.

  已经成功实现了纤溶酶A及其三种立体异构体的首次合成。合成方法涉及酰胺向酮酰胺基团的分子内亲核环化，以产生C-羟基二酮哌嗪骨架。最令人惊讶的发现是，TA的四种立体异构体中的每一种均表现出不同的植物毒，杀真菌和抗病毒活性。
• Binding of Distinct Substrate Conformations Enables Hydroxylation of Remote Sites in Thaxtomin D by Cytochrome P450 TxtC
  作者：Lona M. Alkhalaf、Sarah M. Barry、Dean Rea、Angelo Gallo、Daniel Griffiths、Józef R. Lewandowski、Vilmos Fulop、Gregory L. Challis

  DOI：10.1021/jacs.8b08864

  日期：2019.1.9

  xenobiotic degradation, and natural product biosynthesis. Here we report biochemical, structural, and theoretical studies of TxtC, an unusual bifunctional CYP involved in the biosynthesis of the EPA-approved herbicide thaxtomin A. TxtC was shown to hydroxylate two remote sites within the Phe residue of its diketopiperazine substrate thaxtomin D. The reactions follow a preferred order, with hydroxylation

  细胞色素 P450 (CYPs) 催化药物代谢、异生物质降解和天然产物生物合成中的各种氧化转化。在这里，我们报告了 TxtC 的生化、结构和理论研究，这是一种不寻常的双功能 CYP，参与 EPA 批准的除草剂 thaxtomin A 的生物合成。 TxtC 显示羟基化其二酮哌嗪底物 thaxtomin D 的 Phe 残基内的两个远程位点。反应遵循优选的顺序，在苯基官能化之前α-碳的羟基化。为了阐明远程站点功能化的分子基础，确定了与底物和单羟基化中间体复合的 TxtC 的 X 射线晶体结构。对应于双原子分子（可能是双氧）的电子密度夹在 TxtC 中间体结构中的血红素铁原子和 Thr237 之间，提供了对亚铁-双氧复合物转化为反应性弗利中间体的机制的深入了解。底物和单羟基化中间体在活性位点采用相似的构象，苯基的 π 面位于血红素铁原子上。对接模拟再现了这一观察结果，并确定了第二种能量相似但构象不同的结合模式，其中
• Engineered synthase for production of tryptophan derivatives and intransigent substrates
  申请人：California Institute of Technology

  公开号：US11332729B2

  公开（公告）日：2022-05-17

  This disclosure relates to modified tryptophan synthase and more particularly to modified beta-subunits of tryptophan synthase. The disclosure further relates to cells expressing such modified subunits and methods of producing non-canonical amino acids.

  本公开涉及修饰的色氨酸合成酶，特别是修饰的色氨酸合成酶β亚基。本公开还涉及表达这种修饰亚基的细胞和生产非经典氨基酸的方法。
• Chemistry and Phytotoxicity of Thaxtomin A Alkyl Ethers
  作者：Stuart B. Krasnoff、Emil B. Lobkovsky、Michael J. Wach、Rosemary Loria、Donna M. Gibson

  DOI：10.1021/jf051614w

  日期：2005.11.1

  The thaxtomin phytotoxins (11 and 2) from scab-producing Streptomyces pathogens of the potato are 2,5-dioxopiperazines consisting of modified L-tryptophanyl and L-phenylalanyl units. Thaxtomin A (1) is hydroxylated at C-14, the alpha carbon of the modified L-phenylalanyl moiety. Refluxing thaxtomin A in acidified MeOH, EtOH, and i-PrOH afforded C-14 thaxtomin A methyl- (3a and 3b), ethyl- (4a and 4b), and isopropyl- (5a and 5b) ethers, respectively, in both the 11S,14R (3a, 4a, and 5a) and 11S,14S (3b, 4b, and 5b) configurations. Crystal structures were determined for 3a and 4a. Extensive NMR as well as other spectroscopic data supported structural assignments for all of the derivatives. The 11S,14R-configured derivatives were slightly less potent than the natural products (11 and 2) as inhibitors of lettuce seedling root growth, whereas the activity of the 11S,14S epimers was much reduced, indicating that the configuration at C-14 found in the naturally occurring thaxtomins is essential for biological activity. Among the 11S,14R-configured compounds, potency decreased with an increasing size of the substituted alkoxy group.