13,14β-Dihydro-16,17(E)-didehydro-17-deoxy-9α-O-TBDMS A83543A aglycon 9α-O-TBDMS ether | 155189-84-7

• 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: 13,14β-Dihydro-16,17(E)-didehydro-17-deoxy-9α-O-TBDMS A83543A aglycon 9α-O-TBDMS ether
• 英文别名: (1S,2R,5S,7R,9R,10S,12R,14E,19S)-7-[tert-butyl(dimethyl)silyl]oxy-19-ethyl-14-methyl-20-oxatetracyclo[10.10.0.02,10.05,9]docosa-3,14-diene-13,21-dione
• CAS: 155189-84-7
• 化学式: C₃₀H₄₈O₄Si
• 分子量: 500.794
• InChiKey: CKGFFJHLYLFQJT-UYMVZOODSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.25
• 重原子数：
  35
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  13,14β-Dihydro-16,17(E)-didehydro-17-deoxy-9α-O-TBDMS A83543A aglycon 9α-O-TBDMS ether 在 lithium aluminium tetrahydride 、 双[Α,Α-双(三氟甲基)苯甲醇合]二苯硫 作用下， 以 乙醚 为溶剂， 生成 (E)-(S)-9-[(3S,3aR,5aS,7R,8aR,8bS)-7-(tert-Butyl-dimethyl-silanyloxy)-3-(2-hydroxy-ethyl)-3,3a,5a,6,7,8,8a,8b-octahydro-1H-as-indacen-(2Z)-ylidene]-8-methyl-9-phenyl-non-7-en-3-ol
  参考文献：
  名称：

  多杀菌素 A 的全合成。 2. 涉及纯因子及其完全重组的降解研究

  摘要：

  已实现天然左旋多杀菌素 A (1) 的全合成。第一个目标，即确认先前制备的三环酮 2 的绝对构型分配，是通过 1 中大环内酯环的氧化降解来实现的。该路线开始于实施四步一锅法，从而获得了高效的6 转化为 18。高碘酸盐裂解和过酸氧化事件的组合然后导致 2。在重建阶段，Pd 催化的乙烯基锡烷与酰氯的偶联以对映控制的方式重建了绝大多数结构。一旦实现大环内酯化，首先引入 2,3,4-tri-O-methylrhamnose 单元，并具有非常好的立体控制。最后糖苷化，

  DOI：

  10.1021/ja974010k
• 作为产物：
  描述：

  多杀菌素A苷元 在 2,6-二甲基吡啶 、 sodium tetrahydroborate 、 lithium 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 为溶剂， 反应 2.08h， 生成 13,14β-Dihydro-16,17(E)-didehydro-17-deoxy-9α-O-TBDMS A83543A aglycon 9α-O-TBDMS ether
  参考文献：
  名称：

  Chemistry of A83543A Derivatives. 1. Oxidations and Reductions of A83543A Aglycon

  摘要：

  A retro-biomimetic degradation of the A83543 tetracyclic ring system was investigated as one approach to obtaining putative polyketide-derived, late-stage biosynthetic precursors for the subsequent study of their cyclizations. However, initial studies revealed an unexpected chemical stability of the ring system that required the development of indirect methods to cleave the ring-forming bonds. Hydride reagents were especially useful for reductively cleaving the lactone and generating novel derivatives, whose structures and stereochemistries were determined by detailed NMR analyses correlated with results from molecular modeling. The latter were also used to rationalize the conformational behaviors and lack of reactivities exhibited by the macrocyclic lactone systems in the parent and 13,14-enone-reduced derivatives.

  DOI：

  10.1021/jo00085a049

文献信息

• Total Synthesis of Spinosyn A. 2. Degradation Studies Involving the Pure Factor and Its Complete Reconstitution
  作者：Leo A. Paquette、Iván Collado、Mark Purdie

  DOI：10.1021/ja974010k

  日期：1998.3.1

  A total synthesis of natural levorotatory spinosyn A (1) has been achieved. The first objective, to confirm the absolute configurational assignment of tricyclic ketone 2 prepared earlier, was accomplished by oxidative degradation of the macrocyclic lactone ring in 1. The route began with the implementation of a four-step one-pot process that resulted in the efficient conversion of 6 into 18. A combination

  已实现天然左旋多杀菌素 A (1) 的全合成。第一个目标，即确认先前制备的三环酮 2 的绝对构型分配，是通过 1 中大环内酯环的氧化降解来实现的。该路线开始于实施四步一锅法，从而获得了高效的6 转化为 18。高碘酸盐裂解和过酸氧化事件的组合然后导致 2。在重建阶段，Pd 催化的乙烯基锡烷与酰氯的偶联以对映控制的方式重建了绝大多数结构。一旦实现大环内酯化，首先引入 2,3,4-tri-O-methylrhamnose 单元，并具有非常好的立体控制。最后糖苷化，
• Chemistry of A83543A Derivatives. 1. Oxidations and Reductions of A83543A Aglycon
  作者：Jacek G. Martynow、Herbert A. Kirst

  DOI：10.1021/jo00085a049

  日期：1994.3

  A retro-biomimetic degradation of the A83543 tetracyclic ring system was investigated as one approach to obtaining putative polyketide-derived, late-stage biosynthetic precursors for the subsequent study of their cyclizations. However, initial studies revealed an unexpected chemical stability of the ring system that required the development of indirect methods to cleave the ring-forming bonds. Hydride reagents were especially useful for reductively cleaving the lactone and generating novel derivatives, whose structures and stereochemistries were determined by detailed NMR analyses correlated with results from molecular modeling. The latter were also used to rationalize the conformational behaviors and lack of reactivities exhibited by the macrocyclic lactone systems in the parent and 13,14-enone-reduced derivatives.