oridamycin A | 1224939-45-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: oridamycin A
• 英文别名: (16R,17R,18S,21S)-18-hydroxy-17,21-dimethyl-10-azapentacyclo[11.8.0.03,11.04,9.016,21]henicosa-1,3(11),4,6,8,12-hexaene-17-carboxylic acid
• CAS: 1224939-45-0
• 化学式: C₂₃H₂₅NO₃
• 分子量: 363.456
• InChiKey: XUTJPVCJXVRRLB-IRMYBRCSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  27
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  73.3
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  oridamycin A 、 (R)-methoxytrifluoromethylphenylacetyl chloride 在 吡啶 作用下， 反应 2.0h， 生成 (16R,17R,18S,21S)-17,21-dimethyl-18-[(2S)-3,3,3-trifluoro-2-methoxy-2-phenylpropanoyl]oxy-10-azapentacyclo[11.8.0.03,11.04,9.016,21]henicosa-1,3(11),4,6,8,12-hexaene-17-carboxylic acid
  参考文献：
  名称：

  Oridamycins A and B, Anti-Saprolegnia parasitica Indolosesquiterpenes Isolated from Streptomyces sp. KS84

  摘要：

  Oridamycins A (1) and B (2) were isolated from the fermentation broth of Streptomyces sp. strain KS84 as selective anti-Saprolegnia parasitica antibiotics. Their structures were elucidated as pentacyclic indolosesquiterpenes by the combination of NMR and spectroscopic analyses. The absolute configuration of 1 was determined by ROESY analyses after the advanced Mosher analysis. Compound 1 exhibited anti-S. parasitica activity with an MIC value of 3.0 mu g/mL, but was much less active against the phytopathogenic fungus Phoma sp. and the yeast Saccharomyces cerevisiae.

  DOI：

  10.1021/np1000522
• 作为产物：
  描述：

  (2E,6E)-8-bromo-3,7-dimethylocta-2,6-dienyl acetate 在 sodium cyanide 、 sodium tetrahydroborate 、 乙基溴化镁 、 copper(II) acetate monohydrate 、 manganese(III) triacetate dihydrate 、 sodium hydride 、 戴斯-马丁氧化剂 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 六甲基磷酰三胺 、 乙醚 、 二氯甲烷 、 溶剂黄146 、 二甲基亚砜 、 甲苯 、 mineral oil 为溶剂， 反应 29.17h， 生成 oridamycin A
  参考文献：
  名称：

  Total Synthesis of Oridamycins A and B

  摘要：

  The total synthesis of both oridamycin A and oridamycin B was accomplished starting from a common synthetic intermediate readily prepared from geranyl acetate. The sequence utilizes an oxidative radical cyclization to construct the trans-decalin ring system, setting three of four contiguous stereocenters in one operation. The carbazole nucleus was forged through a one-pot process entailing acid-promoted dehydration followed by 6 pi-electrocyclization/aromatization.

  DOI：

  10.1021/acs.orglett.5b01629

文献信息

• Modular Terpenoid Construction via Catalytic Enantioselective Formation of All-Carbon Quaternary Centers: Total Synthesis of Oridamycin A, Triptoquinones B and C, and Isoiresin
  作者：Jiajie Feng、Florian Noack、Michael J. Krische

  DOI：10.1021/jacs.6b08902

  日期：2016.9.28

  Total syntheses of oridamycin A, triptoquinones B and C, and isoiresin are accomplished from a common intermediate prepared via iridium-catalyzed alcohol C-H tert-(hydroxy)prenylation - a byproduct-free process that forms an all-carbon quaternary stereocenter with excellent control of diastereo- and enantioselectivity.

  Oridamycin A、triptoquinones B 和 C 以及异香豆素的全合成是从通过铱催化的醇 CH 叔-（羟基）异戊二烯化制备的普通中间体完成的 - 一种无副产物的过程，形成一个全碳四元立体中心，具有极好的控制非对映选择性和对映选择性。
• Toward a Unified Total Synthesis of the Xiamycin and Oridamycin Families of Indolosesquiterpenes
  作者：Adam H. Trotta

  DOI：10.1021/acs.joc.7b02623

  日期：2017.12.15

  A variety of strategies were explored to form a chelated radical intermediate en route to xiamycin A, including enolate SET oxidation, oxo-vanadium oxidation, and atom-transfer cyclization. Unfortunately, none of these strategies provided the desired C16-epimeric trans-decalin. Exploratory studies on photoredox-catalyzed radical cyclizations yielded interesting results, including the formation of a

  设计了针对天然产物奥达霉素和厦霉素家族的统一合成策略，旨在从易于从乙酸香叶酯制备的通用合成中间体中获得几种天然产物。该策略的一部分已成功实现，最终合成了奥达霉素A和奥达霉素B。关键步骤包括Mn（III）介导的氧化自由基环化以构建反式-十氢化萘环和6π-电环化/芳香化序列生成2，3-稠合咔唑。奥立霉素B是通过后期的C–H氧化获得的，该氧化将C16甲基转化为羟甲基。探索了多种策略以形成通往霞霉素A的螯合自由基中间体，包括烯醇式SET氧化，氧-钒氧化和原子转移环化。不幸的是，这些策略都没有提供所需的C16-表异构反式-十氢化萘。上photoredox催化自由基环化探索性研究产生了有趣的结果，包括形成从photoredox催化的自由基环化的氧化终止引起的二环内酯，和双6-内与催化剂负载量低至0.01％（摩尔）环化。
• Total Syntheses of Xiamycins A, C, F, H and Oridamycin A and Preliminary Evaluation of their Anti‐Fungal Properties
  作者：Magnus Pfaffenbach、Ian Bakanas、Nicholas R. O'Connor、Jessica L. Herrick、Richmond Sarpong

  DOI：10.1002/anie.201908399

  日期：2019.10.21

  enantiospecific total syntheses of the indolosesquiterpenoids xiamycins A, C, F, H and oridamycin A have been accomplished. The syntheses, which commence from (R)‐carvone, employ a key photoinduced benzannulation sequence to forge the carbazole moiety characteristic of these natural products. Late‐stage diversification from a common intermediate enabled the first syntheses of xiamycins C and F, and an

  吲哚半萜类夏霉素 A、C、F、H 和 Oridamycin A 的发散性和对映特异性全合成已经完成。该合成从 ( R )-香芹酮开始，采用关键的光诱导苯并环化序列来形成这些天然产物的咔唑部分特征。常见中间体的后期多样化使得首次合成了夏霉素 C 和 F，并且意外的一锅氧化脱羧作用（这可能被证明是普遍的）导致了夏霉素 H。所有合成中间体和天然产物都经过了抗真菌测试活动。Xiamycin H 作为三种农业相关真菌病原体的抑制剂而出现。
• Total Synthesis of Oridamycins A and B
  作者：Adam H. Trotta

  DOI：10.1021/acs.orglett.5b01629

  日期：2015.7.2

  The total synthesis of both oridamycin A and oridamycin B was accomplished starting from a common synthetic intermediate readily prepared from geranyl acetate. The sequence utilizes an oxidative radical cyclization to construct the trans-decalin ring system, setting three of four contiguous stereocenters in one operation. The carbazole nucleus was forged through a one-pot process entailing acid-promoted dehydration followed by 6 pi-electrocyclization/aromatization.
• Oridamycins A and B, Anti-<i>Saprolegnia parasitica</i> Indolosesquiterpenes Isolated from <i>Streptomyces</i> sp. KS84
  作者：Kentaro Takada、Hisatsugu Kajiwara、Nobutaka Imamura

  DOI：10.1021/np1000522

  日期：2010.4.23

  Oridamycins A (1) and B (2) were isolated from the fermentation broth of Streptomyces sp. strain KS84 as selective anti-Saprolegnia parasitica antibiotics. Their structures were elucidated as pentacyclic indolosesquiterpenes by the combination of NMR and spectroscopic analyses. The absolute configuration of 1 was determined by ROESY analyses after the advanced Mosher analysis. Compound 1 exhibited anti-S. parasitica activity with an MIC value of 3.0 mu g/mL, but was much less active against the phytopathogenic fungus Phoma sp. and the yeast Saccharomyces cerevisiae.