(±)-epi-gonytolide C

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: (±)-epi-gonytolide C
• 英文别名: epi-gonytolide C；methyl 5-hydroxy-7-methyl-4-oxo-2-(5-oxotetrahydrofuran-2-yl)chromane-2-carboxylate；methyl (2S)-5-hydroxy-7-methyl-4-oxo-2-[(2S)-5-oxooxolan-2-yl]-3H-chromene-2-carboxylate
• 化学式: C₁₆H₁₆O₇
• 分子量: 320.299
• InChiKey: LKWYUESLGBROHL-LRDDRELGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  99.1
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (±)-epi-gonytolide C 在 gold(III) chloride 、 N-溴代丁二酰亚胺(NBS) 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 12.0h， 以65%的产率得到
  参考文献：
  名称：

  Syntheses of Dimeric Tetrahydroxanthones with Varied Linkages: Investigation of “Shapeshifting” Properties

  摘要：

  The 2,4'- and 4,4'-linked variants of the cytotoxic agent secalonic acid A and their analogues have been synthesized. Kinetic resolution of an unprotected tetrahydroxanthone scaffold followed by copper-mediated biaryl coupling allowed for efficient access to these compounds. Evaluation of the "shapeshifting" properties of 2,2'-, 2,4'-, and 4,4'-linked variants of the secalonic acids A in a polar solvent in conjunction with assays of the compounds against select cancer cell lines was conducted to study possible correlations between linkage variation and cytotoxicity.

  DOI：

  10.1021/jacs.5b09825
• 作为产物：
  描述：

  methyl 5-hydroxy-7-methyl-4-oxo-4H-chromene-2-carboxylate 在 2,6-二甲基吡啶 、 sodium tetrahydroborate 、 nickel(II) chloride hexahydrate 、 diisopropylsilanediyl bistriflate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 4.5h， 生成 (±)-epi-gonytolide C
  参考文献：
  名称：

  Vinylogous Addition of Siloxyfurans to Benzopyryliums: A Concise Approach to the Tetrahydroxanthone Natural Products

  摘要：

  A concise approach to the tetrahydroxanthone natural products employing vinylogous addition of siloxyfurans to benzopyryliums and a late-stage Dieckmann cyclization has been developed. With this methodology, chiral, racemic forms of the natural products blennolides B and blennolide C have been synthesized in a maximum of four steps from a 5-hydroxychromone substrate. The regio- and diastereoselectivity of the vinylogous additions was probed using computational studies, which suggested the involvement of Diets Alder-like transition states.

  DOI：

  10.1021/ja110698n

文献信息

• A Domino Approach to the Enantioselective Total Syntheses of Blennolide C and Gonytolide C
  作者：Lutz F. Tietze、Stefan Jackenkroll、Judith Hierold、Ling Ma、Bernd Waldecker

  DOI：10.1002/chem.201402495

  日期：2014.7.7

  established employing a diastereoselective Sharpless dihydroxylation. An extensive survey of (DHQ)‐ and (DHQD)‐based ligands enabled the preparation of both the anti‐isomer 14 a and the syn‐isomer 14 b in very good to reasonable selectivities of 13.7:1 and 1:3.7, respectively. While 14 a was further converted to ent‐3 and ent‐4, 14 b was elaborated to syn‐acid 25 and 2′‐epi‐gonytolide C 28.

  报道了四氢黄酮（-）-布伦内酯C（ent - 4）和相关的γ-内酰胺基苯并二氢呋喃酮（-）-gonytolide C（ent - 3）的第一个对映选择性全合成。合成的关键是对映选择性的多米诺-瓦克/羰基化/甲氧基化反应，以在C-4a处建立立体中心。研究了各种手性BOXAX配体，包括新型（S，S）-i Bu-BOXAX，并允许其获得色烷899％的出色对映选择性。使用非对映选择性的Sharpless二羟基化技术建立了C-4的第二个立体中心。（DHQ）的广泛调查-和（DHQD）基配体使两者的制备反式异构体14和顺式-异构体14b的在很好的13.7合理的选择性：1和1：3.7，分别。而14进一步转化为ENT - 3和ENT - 4，14b中被阐述，以顺式-酸25和2' -表-gonytolideÇ 28。
• A Convergent Synthesis of Gonytolide C Using an Intramolecular Oxa-Michael Addition
  作者：Freda F. Li、Darcy J. Atkinson、Daniel P. Furkert、Margaret A. Brimble

  DOI：10.1002/ejoc.201501402

  日期：2016.2

  of a convergent total synthesis of gonytolide C is reported. The assembly of the natural product core relies on a Horner–Wadsworth–Emmons (HWE) olefination followed by an intramolecular oxa-Michael addition. Robust and efficient preparations of both HWE coupling partners were established. The synthesis enabled further investigation of an asymmetric oxa-Michael cyclisation to prepare gonytolide C, demonstrating

  报告了对 gonytolide C 收敛全合成的演变的完整说明。天然产物核心的组装依赖于 Horner-Wadsworth-Emmons (HWE) 烯化，然后是分子内 oxa-Michael 加成。建立了两个 HWE 耦合伙伴的稳健而有效的准备。该合成能够进一步研究不对称氧杂-迈克尔环化以制备 gonytolide C，证明该策略在合成 2,2-二取代的色满酮中的实用性。
• Total synthesis of gonytolides C and G, lachnone C, and formal synthesis of blennolide C and diversonol
  作者：Gangarajula Sudhakar、Shruthi Bayya、Vilas D. Kadam、Jagadeesh Babu Nanubolu

  DOI：10.1039/c4ob00950a

  日期：——

  The first stereoselective total synthesis of gonytolide C, which is a monomeric unit of an innate immune promoter gonytolide A, has been accomplished from the aldol reaction between acetophenone derived from orcinol and butyrolactone containing α-keto ester followed by the excellent diastereoselective intramolecular cyclization. The first total synthesis of gonytolide G has been achieved by the oxidation

  烯丙内酯C的第一个立体选择性全合成是先天性免疫启动子烯丙内酯A的一个单体单元，这是由衍生自苯二酚的苯乙酮与含有α-酮酸酯的丁内酯之间的醛醇缩合反应完成的，然后进行了出色的非对映选择性分子内环化反应。烯丙内酯C中苄基甲基的氧化已实现了烯丙内酯G的第一个全合成。此外，通过该合成方法已实现了内酯C的全合成以及布兰诺利德C和曲香酚的正式合成。
• Asymmetric Synthesis of Gonytolide A: Strategic Use of an Aryl Halide Blocking Group for Oxidative Coupling
  作者：Xiaowei Wu、Takayuki Iwata、Adam Scharf、Tian Qin、Kyle D. Reichl、John A. Porco

  DOI：10.1021/jacs.8b02535

  日期：2018.5.9

  The first synthesis of the chromanone lactone dimer gonytolide A has been achieved employing vanadium(V)-mediated oxidative coupling of the monomer gonytolide C. An o-bromine blocking group strategy was employed to favor para- para coupling and to enable kinetic resolution of (±)-gonytolide C. Asymmetric conjugate reduction enabled practical kinetic resolution of a chiral, racemic precursor and the

  色满酮内酯二聚体 gonytolide A 的首次合成是利用钒 (V) 介导的单体 gonytolide C 的氧化偶联实现的。采用邻溴封闭基团策略有利于对位偶联并实现 ( ±)-gonytolide C。不对称缀合物还原能够实现手性、外消旋前体的实际动力学拆分以及 (+)-gonytolide A 及其阻转异构体的不对称合成。
• Atropselective syntheses of (−) and (+) rugulotrosin A utilizing point-to-axial chirality transfer
  作者：Tian Qin、Sarah L. Skraba-Joiner、Zeinab G. Khalil、Richard P. Johnson、Robert J. Capon、John A. Porco

  DOI：10.1038/nchem.2173

  日期：2015.3

  Chiral, dimeric natural products containing complex structures and interesting biological properties have inspired chemists and biologists for decades. A seven-step total synthesis of the axially chiral, dimeric tetrahydroxanthone natural product rugulotrosin A is described. The synthesis employs a one-pot Suzuki coupling/dimerization to generate the requisite 2,2′-biaryl linkage. Highly selective

  数十年来，具有复杂结构和有趣生物学特性的手性二聚体天然产物激发了化学家和生物学家的灵感。描述了轴向手性二聚四氢x吨酮天然产物古格罗辛A的七步全合成。合成过程采用一锅Suzuki偶联/二聚生成必要的2,2'-联芳基键。使用具有非手性膦配体的钯催化，可以实现高度选择性的点对轴手性转移。获得了单一的X射线晶体衍射数据，以确认鲁古洛辛A的阻转异构体构型和绝对立体化学。描述了计算研究以合理化关键二聚化步骤中观察到的阻转选择性。