ent-10β,13-dihydroxy-3-oxo-20-norgibberella-1,6-diene-7,19-dioic acid 19,10β-lactone 7-methyl ester | 5034-25-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: ent-10β,13-dihydroxy-3-oxo-20-norgibberella-1,6-diene-7,19-dioic acid 19,10β-lactone 7-methyl ester
• 英文别名: 3-dehydro gibberellin A₃ methylester；keto-gibberellic acid methyl ester；3-dehydro-GA₁；JRA-003；4a,7-dihydroxy-1β-methyl-8-methylen-2-oxo-4aα,7β-gibb-3-ene-1α,10β-dicarboxylic acid-1=>4a lactone-10-methyl ester；4a,7-Dihydroxy-1β-methyl-8-methylen-2-oxo-4aα,7β-gibb-3-en-1α,10β-dicarbonsaeure-1=>4a-lacton-10-methylester；methyl (1R,2R,5S,8S,9S,10R,11S)-5-hydroxy-11-methyl-6-methylidene-12,16-dioxo-15-oxapentacyclo[9.3.2.15,8.01,10.02,8]heptadec-13-ene-9-carboxylate
• CAS: 5034-25-3
• 化学式: C₂₀H₂₂O₆
• 分子量: 358.391
• InChiKey: QRSFVDXLKQNKHW-WIKFVNKQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  89.9
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ent-10β,13-dihydroxy-3-oxo-20-norgibberella-1,6-diene-7,19-dioic acid 19,10β-lactone 7-methyl ester 在 sodium tetrahydroborate 、 对甲苯磺酸 、 lithium bromide 作用下， 以 二乙二醇二甲醚 为溶剂， 反应 25.0h， 生成 Gibberellin A1 methyl ester 13-acetate
  参考文献：
  名称：

  Beale, Michael H.; MacMillan, Jake, Journal of the Chemical Society. Perkin transactions I, 1980, p. 877 - 884

  摘要：

  DOI：
• 作为产物：
  描述：

  赤霉素A3甲酯 在 四丙基高钌酸铵 、 N-甲基吗啉氧化物 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 4.0h， 以80.5%的产率得到ent-10β,13-dihydroxy-3-oxo-20-norgibberella-1,6-diene-7,19-dioic acid 19,10β-lactone 7-methyl ester
  参考文献：
  名称：

  Synthesis and biological evaluation of pharbinilic acid and derivatives as NF-κB pathway inhibitors

  摘要：

  报道了一种合成法尔比利酸的7步法，该酸是赤霉素天然产物家族的成员，也是第一个自然存在的异赤霉酸。

  DOI：

  10.1039/c5cc02918j

文献信息

• Reaction of methyl gibberellate with triphenylphosphine and carbon tetrachloride
  作者：James Z. Duri、Braulio M. Fraga、James R. Hanson

  DOI：10.1039/p19810003016

  日期：——

  Treatment of methyl gibberellate and its 3-epimer with triphenylphosphine and carbon tetrachloride containing acetone or pyridine, gave the 1β-chloro- and 1β,13-dichloro-Δ2-derivatives respectively as the major products. The 3-chloro-compounds were obtained as minor products. The 1-bromo-compounds were obtained with carbon tetrabromide. The structures of these compounds were established by location

  甲基gibberellate和其3-差向异构体用含有丙酮或吡啶三苯基膦和四氯化碳的处理，得到1β氯和1β，13二氯Δ 2分别-衍生物作为主要产品。得到的3-氯化合物为次要产物。用四溴化碳获得1-溴化合物。通过标签的位置，在产品从3-确立了这些化合物的结构外延[3β- - 2 H] gibberellate。
• Preparation of gibberellins A9 and A20 from gibberellic acid
  作者：Zvitendo J. Duri、Braulio M. Fraga、James R. Hanson

  DOI：10.1039/p19810000161

  日期：——

  using triphenylphosphine and carbon tetrachloride. Hydrogenolysis of the chlorides with tributyltin hydride afforded gibberellins A20 and A9 as their methyl esters. Gibberellin A9 methyl ester was also prepared from the gibberellin A4/A7 mixture. The stereochemistry of the conjugate reduction of the ring-A-unsaturated ketone is defined.

  使用三苯膦和四氯化碳，赤霉酸甲酯已通过3-epigibberellin A 1的甲酯转化为3β-氯代和3β，13-二氯代衍生物。用氢化三丁基锡氢化氯化物，得到赤霉素A 20和A 9为它们的甲酯。赤霉素A 9甲酯也由赤霉素A 4 / A 7混合物制备。定义了环A-不饱和酮的共轭还原的立体化学。
• Gibberellins—LXXXIX
  作者：B. Voigt、G. Adam

  DOI：10.1016/s0040-4020(01)88545-8

  日期：1983.1

  The synthesis of a series of 1-oxygenated gibberellins starting from GA3 (1) is described. Nucleophilic addition of hydrazoic acid to 3-dehydro GA3 (2) was followed by NaBH4 reduction of the resulting 1 -azido-3-ketones 4 and 5 to the corresponding azido alcohols 8–10, and photolysis of the latter compounds to instable 1-imines which were smoothly hydrolysed to the 1-oxo-3-hydroxy gibberellins 13 and

  描述了从GA 3（1）开始的一系列1-氧化赤霉素的合成。向3-脱氢GA 3（2）中亲核地添加氢氰酸，然后将NaBH 4将所得的1-叠氮基3-酮4和5还原为相应的叠氮基醇8-10，然后将后者化合物光解为不稳定的1-亚胺被平滑地水解为1-oxo-3-羟基赤霉素13和14。随后的NaBH 4还原导致GA 57（19）和GA 55（20）及其3个顶点，分别为17和18。在进一步的步骤中，将1-oxo-GA 5（21），1α-和1β-羟基-GA 5（23 1-oxo-GA 20（25）以及1α-和1β-羟基-GA 20（26和27）分别为关于C-1和C-3的立体化学，通过物理数据确定合成的赤霉素的结构，尤其是基于1 H NMR和ORD测量。
• The stereochemistry of reduction of A gibberellin Δ¹-unsaturated ketone
  作者：Zvitendo J. Duri、James R. Hanson

  DOI：10.1039/p19840000363

  日期：——

  Whilst sodium borodeuteride reduction of gibberellin A3 3-ketone which affords gibberellin A1, and its 3-epimer, proceeds stereospecifically from the β-face at C-1, the reaction has only limited stereoselectivity at C-2 affording in the case of 3-epi-gibberellin A1, methyl ester, a 2α: 2β-2H ratio of 0.35–0.5:1 thus revising a previous conclusion.

  硼氢化钠还原的赤霉素A 3 3-酮（提供赤霉素A 1和其3-表异构体）在C-1处从β面立体定向地进行，而在C-2时，该反应仅在C-2处具有有限的立体选择性，而在3- epi- gibberellin A 1，甲酯，2α：2β- 2 H比为0.35–0.5：1，因此修改了先前的结论。
• Complex and structurally diverse compounds
  申请人：The Board of Trustees of the University of Illinois

  公开号：US10800730B2

  公开（公告）日：2020-10-13

  The invention provides a novel, general, and facile strategy for the creation of small molecules with high structural and stereochemical complexity. Aspects of the methods include ring system distortion reactions that are systematically applied to rapidly convert readily available natural products to structurally complex compounds with diverse molecular architectures. Through evaluation of chemical properties including fraction of sp3 carbons, ClogP, and the number of stereogenic centers, these compounds are shown to be significantly more complex and diverse than those in standard screening collections. This approach is demonstrated with natural products (gibberellic acid, adrenosterone, and quinine) from three different structural classes, and methods are described for the application of this strategy to any suitable natural product.

  本发明提供了一种新颖、通用和简便的策略，用于制造具有高结构和立体化学复杂性的小分子。该方法的各个方面包括系统地应用环系畸变反应，将容易获得的天然产物快速转化为具有不同分子结构的结构复杂的化合物。通过对化学特性（包括 sp3 碳的比例、ClogP 和立体中心的数量）进行评估，这些化合物的复杂性和多样性明显高于标准筛选集合中的化合物。该方法通过三种不同结构类别的天然产物（赤霉素、肾上腺甾酮和奎宁）进行了演示，并介绍了将该策略应用于任何合适的天然产物的方法。