(4E,6Z,8S,9E,11S,12R,13R,14S,16R)-19-(azetidin-1-yl)-13-hydroxy-8,14-dimethoxy-4,10,12,16-tetramethyl-11-sulfanyl-2-azabicyclo[16.3.1]docosa-1(21),4,6,9,18-pentaene-3,20,22-trione | 155630-43-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酰胺类
• 英文名称: (4E,6Z,8S,9E,11S,12R,13R,14S,16R)-19-(azetidin-1-yl)-13-hydroxy-8,14-dimethoxy-4,10,12,16-tetramethyl-11-sulfanyl-2-azabicyclo[16.3.1]docosa-1(21),4,6,9,18-pentaene-3,20,22-trione
• CAS: 155630-43-6
• 化学式: C₃₀H₄₂N₂O₆S
• 分子量: 558.739
• InChiKey: RUAOYSKXRVBINW-ZDWBIVHOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  39
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  106
• 氢给体数：
  3
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (4E,6Z,8S,9E,11S,12R,13R,14S,16R)-19-(azetidin-1-yl)-13-hydroxy-8,14-dimethoxy-4,10,12,16-tetramethyl-11-sulfanyl-2-azabicyclo[16.3.1]docosa-1(21),4,6,9,18-pentaene-3,20,22-trione 在 potassium tert-butylate 、 氨 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 17.92h， 生成 17-Azetidinyl-7-thioureido-7-decarbamoyl-17-demethoxygeldanamycin
  参考文献：
  名称：

  Tandem [3,3]-Sigmatropic Rearrangements in an Ansamycin: Stereospecific Conversion of an (S)-Allylic Alcohol to an (S)-Allylic Amine Derivative

  摘要：

  Ansamycin ring modifications in the geldanamycin oncogene inhibitor series were investigated. A carbamate to urea interchange was accomplished with net retention at the 7(S)-center of a geldanamycin analog. This chirally specific transformation was efficiently accomplished by employing tandem [3,3]-sigmatropic rearrangements involving first, the conversion of the allylic 7(S)-alcohol 2b to an allylic 9(S)-thiol, 4b, and then the rearrangement to the allylic 7(S)-isothiocyanate 6, which was carried on to allylic 7(S)-amine derivatives 1a and 1b. This tandem rearrangement strategy may have wide applicability for the preparation of chiral allylic amines from the large array of readily available chiral allylic alcohols.

  DOI：

  10.1021/jo00088a047
• 作为产物：
  描述：

  格尔德霉素 在 potassium tert-butylate 、 氨 作用下， 以 乙醇 、 二氯甲烷 、 二甲基亚砜 、 乙腈 为溶剂， 反应 54.0h， 生成 (4E,6Z,8S,9E,11S,12R,13R,14S,16R)-19-(azetidin-1-yl)-13-hydroxy-8,14-dimethoxy-4,10,12,16-tetramethyl-11-sulfanyl-2-azabicyclo[16.3.1]docosa-1(21),4,6,9,18-pentaene-3,20,22-trione
  参考文献：
  名称：

  Tandem [3,3]-Sigmatropic Rearrangements in an Ansamycin: Stereospecific Conversion of an (S)-Allylic Alcohol to an (S)-Allylic Amine Derivative

  摘要：

  Ansamycin ring modifications in the geldanamycin oncogene inhibitor series were investigated. A carbamate to urea interchange was accomplished with net retention at the 7(S)-center of a geldanamycin analog. This chirally specific transformation was efficiently accomplished by employing tandem [3,3]-sigmatropic rearrangements involving first, the conversion of the allylic 7(S)-alcohol 2b to an allylic 9(S)-thiol, 4b, and then the rearrangement to the allylic 7(S)-isothiocyanate 6, which was carried on to allylic 7(S)-amine derivatives 1a and 1b. This tandem rearrangement strategy may have wide applicability for the preparation of chiral allylic amines from the large array of readily available chiral allylic alcohols.

  DOI：

  10.1021/jo00088a047

文献信息

• Tandem [3,3]-Sigmatropic Rearrangements in an Ansamycin: Stereospecific Conversion of an (S)-Allylic Alcohol to an (S)-Allylic Amine Derivative
  作者：Rodney C. Schnur、Michael L. Corman

  DOI：10.1021/jo00088a047

  日期：1994.5

  Ansamycin ring modifications in the geldanamycin oncogene inhibitor series were investigated. A carbamate to urea interchange was accomplished with net retention at the 7(S)-center of a geldanamycin analog. This chirally specific transformation was efficiently accomplished by employing tandem [3,3]-sigmatropic rearrangements involving first, the conversion of the allylic 7(S)-alcohol 2b to an allylic 9(S)-thiol, 4b, and then the rearrangement to the allylic 7(S)-isothiocyanate 6, which was carried on to allylic 7(S)-amine derivatives 1a and 1b. This tandem rearrangement strategy may have wide applicability for the preparation of chiral allylic amines from the large array of readily available chiral allylic alcohols.