(9Z,11E)-(4R,6R,8R)-17,19-Bis-(tert-butyl-dimethyl-silanyloxy)-16-chloro-4-methyl-3,7-dioxa-tricyclo[13.4.0.0^6,8]nonadeca-1(15),9,11,16,18-pentaene-2,13-dione | 140480-16-6

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: (9Z,11E)-(4R,6R,8R)-17,19-Bis-(tert-butyl-dimethyl-silanyloxy)-16-chloro-4-methyl-3,7-dioxa-tricyclo[13.4.0.0^6,8]nonadeca-1(15),9,11,16,18-pentaene-2,13-dione
• CAS: 140480-16-6
• 化学式: C₃₀H₄₅ClO₆Si₂
• 分子量: 593.308
• InChiKey: KDBFNQLUSQJNOQ-PAUCVUCJSA-N

物化性质

• 沸点：
  631.9±55.0 °C(Predicted)
• 密度：
  1.068±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.05
• 重原子数：
  39.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  74.36
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (9Z,11E)-(4R,6R,8R)-17,19-Bis-(tert-butyl-dimethyl-silanyloxy)-16-chloro-4-methyl-3,7-dioxa-tricyclo[13.4.0.0^6,8]nonadeca-1(15),9,11,16,18-pentaene-2,13-dione 在 甲醇 、 borax buffer 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 根赤壳菌素
  参考文献：
  名称：

  Convergent stereospecific total synthesis of monocillin I and radicicol: some simplifications and improvements

  摘要：

  A much improved and reliable access to the macrolide 9, key-intermediate in our synthesis of monocillin I and radicicol is reported, via a modification of our first synthesis. The formation of the conjugated E.Z-dienone trans-epoxide is now achieved in a much higher yield, in a stereospecific reaction, by elimination of the methanesulfonate ester of the 6'-OH of the intermediate macrolide. It is also shown that the configuration of the 6'-OH has no significant incidence on all the steps leading to 9, and that consequently the two diastereoisomers 12, epimeric at 6', can be used for the synthesis of radicicol. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)00713-x
• 作为产物：
  描述：

  6,8-Bis-(tert-butyl-dimethyl-silanyloxy)-3-chloromethyl-isochromen-1-one 在 吡啶 、 sodium chlorite 、 sodium dihydrogenphosphate 、 i-Pr₂NEt₂ 、 二异丁基氢化铝 、 甲基磺酰氯 、 三乙胺 、 三苯基膦 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 叔丁醇 为溶剂， 反应 12.75h， 生成 (9Z,11E)-(4R,6R,8R)-17,19-Bis-(tert-butyl-dimethyl-silanyloxy)-16-chloro-4-methyl-3,7-dioxa-tricyclo[13.4.0.0^6,8]nonadeca-1(15),9,11,16,18-pentaene-2,13-dione
  参考文献：
  名称：

  Convergent stereospecific total synthesis of monocillin I and radicicol: some simplifications and improvements

  摘要：

  A much improved and reliable access to the macrolide 9, key-intermediate in our synthesis of monocillin I and radicicol is reported, via a modification of our first synthesis. The formation of the conjugated E.Z-dienone trans-epoxide is now achieved in a much higher yield, in a stereospecific reaction, by elimination of the methanesulfonate ester of the 6'-OH of the intermediate macrolide. It is also shown that the configuration of the 6'-OH has no significant incidence on all the steps leading to 9, and that consequently the two diastereoisomers 12, epimeric at 6', can be used for the synthesis of radicicol. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)00713-x

文献信息

• Halohydrin and Oxime Derivatives of Radicicol: Synthesis and Antitumor Activities
  作者：Tsutomu Agatsuma、Harumi Ogawa、Kazuhito Akasaka、Akira Asai、Yoshinori Yamashita、Tamio Mizukami、Shiro Akinaga、Yutaka Saitoh

  DOI：10.1016/s0968-0896(02)00260-2

  日期：2002.11

  Novel halohydrin and oxime derivatives of radicicol (1) were prepared and evaluated for their v-src tyrosine kinase inhibitory, antiproliferative, and antitumor activities. Some of the resulting derivatives showed significantly improved antitumor activities than those of 1 in vitro as tested in a cell proliferation assay and in vivo using sc-inoculated human breast carcinoma and epidermoid tumor models

  制备了Radicicol（1）的新型卤代醇和肟衍生物，并对其v-src酪氨酸激酶抑制，抗增殖和抗肿瘤活性进行了评估。如在细胞增殖试验中和在体外使用皮下注射的人乳腺癌和表皮样肿瘤模型所测试的，某些所得衍生物显示出比1更高的抗肿瘤活性。还描述了基于radicicol的新型亲和探针的设计和合成。
• Convergent stereospecific total synthesis of Monocillin I and Monorden (or Radicicol)
  作者：Maxime Lampilas、Robert Lett

  DOI：10.1016/s0040-4039(00)77713-6

  日期：1992.2

  The first total syntheses of the antifungal resorcylic macrolides Monocillin I and Monorden (or Radicicol) have been achieved by a convergent stereospecific route. TBDMS phenol ethers were found to be suitable for all the scheme and were removed in the ultimate step under mild conditions (aqueous borax/THF/methanol), hence allowing to get the natural macrolides in good yields, with no degradation.

  抗真菌间苯二酚大环内酯类Monocillin I和Monorden（或Radicicol）的第一个总合成已通过收敛的立体定向途径实现。发现TBDMS酚醚适用于所有方案，并在温和的条件下（硼砂/ THF /甲醇水溶液）在最终步骤中除去，因此能够以高收率得到天然大环内酯类，而没有降解。还报道了将双-OTBMDS Monocillin I有效转化为莫诺登。