13,14α-Dihydro-21(S)-hydroxy-1,21-seco-(3β-H)-3α-(2-hydroxyethyl) A83543A aglycon 9α,17(S)-bis-O-(TBDMS) ether

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 13,14α-Dihydro-21(S)-hydroxy-1,21-seco-(3β-H)-3α-(2-hydroxyethyl) A83543A aglycon 9α,17(S)-bis-O-(TBDMS) ether
• 英文别名: (2R,3S,7S)-1-[(2S,3S,3aR,5aS,7R,8aR,8bS)-7-[tert-butyl(dimethyl)silyl]oxy-3-(2-hydroxyethyl)-1,2,3,3a,5a,6,7,8,8a,8b-decahydro-as-indacen-2-yl]-3-[tert-butyl(dimethyl)silyl]oxy-7-hydroxy-2-methylnonan-1-one
• 化学式: C₃₆H₆₈O₅Si₂
• 分子量: 637.104
• InChiKey: LWVNEMLNMFPFDF-WPHPRKDWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.76
• 重原子数：
  43
• 可旋转键数：
  16
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  76
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  多杀菌素 在 2,6-二甲基吡啶 、 lithium aluminium tetrahydride 、 硫酸 作用下， 以 乙醚 、 乙醇 、 二氯甲烷 为溶剂， 反应 5.58h， 生成 13,14α-Dihydro-21(S)-hydroxy-1,21-seco-(3β-H)-3α-(2-hydroxyethyl) A83543A aglycon 9α,17(S)-bis-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

• 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.