6-(tert-Butyl-dimethyl-silanyloxy)-8-hydroxy-3-[(E)-4-[(2S,3R)-3-((S)-2-hydroxy-propyl)-oxiranyl]-4-(4-methoxy-benzyloxy)-but-2-enyl]-isochromen-1-one | 459145-00-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮
• 英文名称: 6-(tert-Butyl-dimethyl-silanyloxy)-8-hydroxy-3-[(E)-4-[(2S,3R)-3-((S)-2-hydroxy-propyl)-oxiranyl]-4-(4-methoxy-benzyloxy)-but-2-enyl]-isochromen-1-one
• 英文别名: 6-[tert-butyl(dimethyl)silyl]oxy-8-hydroxy-3-[(E)-4-[(2S,3R)-3-[(2S)-2-hydroxypropyl]oxiran-2-yl]-4-[(4-methoxyphenyl)methoxy]but-2-enyl]isochromen-1-one
• CAS: 459145-00-7
• 化学式: C₃₂H₄₂O₈Si
• 分子量: 582.766
• InChiKey: IJZABNJTKCNLMT-IWPYEKHSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.11
• 重原子数：
  41
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  107
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  6-(tert-Butyl-dimethyl-silanyloxy)-8-hydroxy-3-[(E)-4-[(2S,3R)-3-((S)-2-hydroxy-propyl)-oxiranyl]-4-(4-methoxy-benzyloxy)-but-2-enyl]-isochromen-1-one 在 吡啶 、 sodium chlorite 、 sodium dihydrogenphosphate 、 i-Pr₂NEt₂ 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 、 叔丁醇 为溶剂， 反应 11.0h， 生成 (E)-(4R,6R,8S)-17,19-Bis-(tert-butyl-dimethyl-silanyloxy)-9-(4-methoxy-benzyloxy)-4-methyl-3,7-dioxa-tricyclo[13.4.0.0^6,8]nonadeca-1(15),10,16,18-tetraene-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
• 作为产物：
  描述：

  6,8-Bis-(tert-butyl-dimethyl-silanyloxy)-3-chloromethyl-isochromen-1-one 在 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.75h， 生成 6-(tert-Butyl-dimethyl-silanyloxy)-8-hydroxy-3-[(E)-4-[(2S,3R)-3-((S)-2-hydroxy-propyl)-oxiranyl]-4-(4-methoxy-benzyloxy)-but-2-enyl]-isochromen-1-one
  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

• Improvements of the total synthesis of monocillin I and radicicol via Miyaura–Suzuki couplings
  作者：Isabelle Tichkowsky、Robert Lett

  DOI：10.1016/s0040-4039(02)00714-1

  日期：2002.5

  The palladium-catalyzed coupling of the vinyldisiamylborane, formed in situ, affords the isocoumarins which can be used further for the synthesis of radicicol and related macrolides, in 72% global overall yield from the alkyne. Advantages over related vinylboronates or vinyltin couplings are discussed in the case of the present examples.

  原位形成的乙烯基二亚氨基硼烷的钯催化偶联提供了异香豆素，其可以进一步用于合成紫杉醇和相关的大环内酯类，炔烃的全球总产率为72％。在本实施例的情况下，讨论了相对于相关的乙烯基硼酸酯或乙烯基锡偶联剂的优点。