macrosphelide I | 398143-65-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: macrosphelide I
• 英文别名: (4R,7E,9R,10S,15R,16S)-9,15-dihydroxy-4,10,16-trimethyl-1,5,11-trioxacyclohexadec-7-ene-2,6,12-trione
• CAS: 398143-65-2
• 化学式: C₁₆H₂₄O₈
• 分子量: 344.362
• InChiKey: KIBZGGIVYAKKPJ-VGOUJBTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  119
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  macrosphelide I 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 以81%的产率得到(4R,7E,10S,16S)-4,10,16-trimethyl-1,5,11-trioxacyclohexadec-7-ene-2,6,9,12,15-pentone
  参考文献：
  名称：

  寻找新的细胞凋亡诱导剂的人工合成大环内酯类化合物的设计，合成和生物学评估

  摘要：

  分为两半的药物：设计并合成了由大酚核骨架和埃坡霉素侧链组成的新型人工化合物。这些化合物比亲本自然型大环硫醚更有力地诱导细胞凋亡。

  DOI：

  10.1002/chem.200802661
• 作为产物：
  描述：

  (1S,2R)-2-[1-(tert-butyl)-1,1-dimethylsilyl]oxy-1-methyl-3-butenyl (4R,5S)-4-[1-(tert-butyl)-1,1-dimethylsilyl]oxy-5-hydroxyhexanoate 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 4-二甲氨基吡啶 、 氟化氢吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 54.0h， 生成 macrosphelide I
  参考文献：
  名称：

  RCM mediated synthesis of macrosphelides I and G

  摘要：

  The total synthesis of 16-membered macrolides, macraosphelides I and G, has been achieved starting from ethyl-(S)-lactate and (S)- malic acid. A combination of Jacobsen's hydrolytic kinetic resolution and Sharpless epoxidation is used for the creation of two stereogenic centres, while Yamaguchi esterification and ring-closing metathesis strategies were used for the construction of the lactone ring. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2007.08.017

文献信息

• Absolute stereostructures of cell-adhesion inhibitors, macrosphelides C, E–G and I, produced by a Periconia species separated from an Aplysia sea hare
  作者：Takeshi Yamada、Masashi Iritani、Mitsunobu Doi、Katsuhiko Minoura、Tadayoshi Ito、Atsushi Numata

  DOI：10.1039/b104337b

  日期：2001.11.15

  Macrosphelides E–I have been isolated, along with known macrosphelides A and C, from a strain of Periconia byssoides originally separated from the sea hare Aplysia kurodai, and the absolute stereostructures of macrosphelides E–G and I have been elucidated on the basis of spectroscopic analyses using 1D and 2D NMR techniques and some chemical transformations. In addition, the absolute configuration of macrosphelide C, previously undetermined, has been established by X-ray analysis and application of the modified Mosher method. Macrosphelides E–H inhibited the adhesion of human-leukaemia HL-60 cells to HUVEC.

  宏球苷E–I与已知的宏球苷A和C一起从最初从海兔Aplysia kurodai分离出的Periconia byssoides菌株中提取出来，并且宏球苷E–G和I的绝对立体结构已通过使用1D和2D NMR技术的光谱分析及一些化学转化进行阐明。此外，之前未确定的宏球苷C的绝对构型已通过X射线分析和改良的Mosher方法确立。宏球苷E–H抑制了人类白血病HL-60细胞与HUVEC的粘附。
• Stereoselective Synthesis of Macrosphelide I
  作者：Bacchu Veena、Gangavaram Sharma

  DOI：10.1055/s-0033-1338657

  日期：——

  macrosphelide I, has been achieved starting from commercially available chiral materials, ethyl ( S )-lactate and methyl ( R )-3-hydroxybutyrate. Titanium(IV) promoted the regioselective nucleophilic opening reaction of epoxy alcohol with benzoic acid, Sharpless epoxidation, ring-closing metathesis and Yamaguchi esterification as key steps for the construction of the 16-membered macrotriolide.

  从市售的手性材料、(S)-乳酸乙酯和(R)-3-羟基丁酸甲酯开始，已经实现了macrosphelide I的有效全合成。钛 (IV) 促进了环氧醇与苯甲酸的区域选择性亲核开环反应、Sharpless 环氧化、闭环复分解和 Yamaguchi 酯化，这是构建 16 元大三内酯的关键步骤。
• Design, Synthesis, and Biological Evaluation of Artificial Macrosphelides in the Search for New Apoptosis-Inducing Agents
  作者：Yuji Matsuya、Yuta Kobayashi、Takanori Kawaguchi、Ayana Hori、Yuka Watanabe、Kentaro Ishihara、Kanwal Ahmed、Zheng-Li Wei、Da-Yong Yu、Qing-Li Zhao、Takashi Kondo、Hideo Nemoto

  DOI：10.1002/chem.200802661

  日期：2009.6.2

  A drug of two halves: New artificial compounds composed of a macrosphelide core skeleton and an epothilone side chain were designed and synthesized. These compounds were more potent inducers of apoptosis than the parent natural‐type macrosphelides.

  分为两半的药物：设计并合成了由大酚核骨架和埃坡霉素侧链组成的新型人工化合物。这些化合物比亲本自然型大环硫醚更有力地诱导细胞凋亡。
• RCM mediated synthesis of macrosphelides I and G
  作者：Gangavaram V.M. Sharma、Kagita Veera Babu

  DOI：10.1016/j.tetasy.2007.08.017

  日期：2007.9

  The total synthesis of 16-membered macrolides, macraosphelides I and G, has been achieved starting from ethyl-(S)-lactate and (S)- malic acid. A combination of Jacobsen's hydrolytic kinetic resolution and Sharpless epoxidation is used for the creation of two stereogenic centres, while Yamaguchi esterification and ring-closing metathesis strategies were used for the construction of the lactone ring. (c) 2007 Elsevier Ltd. All rights reserved.