(3S,4S,5R)-6-[(tert-butyldimethylsilyl)oxy]-4-(methoxymethoxy)-2,5-dimethyl-3-hexanol acetate | 126587-53-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (3S,4S,5R)-6-[(tert-butyldimethylsilyl)oxy]-4-(methoxymethoxy)-2,5-dimethyl-3-hexanol acetate
• 英文别名: [(3S,4S,5R)-6-[tert-butyl(dimethyl)silyl]oxy-4-(methoxymethoxy)-2,5-dimethylhexan-3-yl] acetate
• CAS: 126587-53-9
• 化学式: C₁₈H₃₈O₅Si
• 分子量: 362.582
• InChiKey: XZLGXEOAMAPIHW-PVAVHDDUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.22
• 重原子数：
  24
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3S,4S,5R)-6-[(tert-butyldimethylsilyl)oxy]-4-(methoxymethoxy)-2,5-dimethyl-3-hexanol acetate 在 2,6-二甲基吡啶 、 钾硼氢 、 lithium diisopropyl amide 作用下， 以 乙醇 为溶剂， 生成 (3R,4R,5S)-4-<<(benzyloxy)carbonyl>amino>-3-<(triisopropylsilyl)oxy>-5-methyl-heptanoic acid, (1S,2S,3R)-4-<(tert-butyldimethylsilyl)oxy>-1-isopropyl-2-(methoxymethoxy)-3-methylbutyl ester
  参考文献：
  名称：

  双氢精蛋白的合成研究。IV。大环的合成

  摘要：

  描述了在双氢精蛋白中发现的到23元大环的立体控制途径。

  DOI：

  10.1016/s0040-4039(01)80647-x
• 作为产物：
  描述：

  L-缬氨酸 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 三氟甲磺酸 、 硫酸 、 氨 、 sodium 、 三氧化硫吡啶 、 四氯化锡 、 三乙胺 、 N,N-二异丙基乙胺 、 sodium nitrite 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 环己烷 、 水 、 二甲基亚砜 为溶剂， 反应 69.0h， 生成 (3S,4S,5R)-6-[(tert-butyldimethylsilyl)oxy]-4-(methoxymethoxy)-2,5-dimethyl-3-hexanol acetate
  参考文献：
  名称：

  didemnins A、B 和 C 的全合成和结构研究

  摘要：

  Didemnins A、B 和 C 以立体控制的方式有效制备，产生常见的大环，并在单独的步骤中，在 L-苏氨酸的氨基上引入取代基作为光学纯单元。我们设想 L-亮氨酸和 HIP 基团 (2S,4S) 之间以及 L-苏氨酸和异司他汀 (3S,4R,5S) 之间的断开将提供两个单元：HIP-异司他汀单元 (I) 和四肽单元 (II) )

  DOI：

  10.1021/ja00177a030

文献信息

• Synthesis of New Didemnin B Analogs for Investigations of Structure/Biological Activity Relationships
  作者：Scott C. Mayer、Joshi Ramanjulu、Matthew D. Vera、Amy J. Pfizenmayer、Madeleine M. Joullie

  DOI：10.1021/jo00097a022

  日期：1994.9

  Modifications were introduced in the side chain of didemnin B to afford several analogs (1f-1j) for biological testing in order to identify the features responsible for the bioactivity of the natural products (1a-1c). To achieve our goal, two changes were made in the proline ring of the beta-turn side chain. Initially, a hydroxyl group was incorporated at the C-4 position of the ring to increase the polar nature of the molecule. Secondly, unsaturation was introduced at C-3 and C-4 to increase the rigidity of the ring and to provide a site for tritiation to follow the drug pathway in biological systems. Improvements were also introduced in the macrocycle construction to produce gram quantities of this unit (1d) for the preparation of the planned analogs. The linear precursor to the macrocycle was oxidized more effectively with 1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one (Dess-Martin periodinane reagent), and cyclization yields were increased substantially by using a new coupling reagent, pentafluorophenyl diphenylphosphinate (FDPP). (1H-1,2,3-benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate (BOP) and pentafluorophenyl trifluoroacetate were also used to improve other coupling reactions.
• Synthesis of a Reduced Ring Analog of Didemnin B
  作者：Joshi M. Ramanjulu、Xiaobin Ding、Madeleine M. Joullié、Wen-Ren Li

  DOI：10.1021/jo9623696

  日期：1997.7.1

  As part of investigations directed toward the determination of the essential/nonessential structural features for the bioactivities of didemnin B, we designed a reduced ring analog in which three moieties, namely the tyrosine side chain, the isostatine hydroxyl, and the side chain (L-lactyl-L-prolyl-N-Me-D-leucine), were in their presumed bioactive conformation. In designing the reduced ring analog, we eliminated the leucine-proline portion of the macrocycle core and replaced if with an n-butyl linker in order to elucidate its role. According to MM2 calculations (MacroModel molecular modeling), this analog was of lower energy than the natural product didemnin B, and both structures were superimposable. The synthetic strategy involved four disconnections. Macrocyclization was accomplished at the activated carboxylic acid of the alpha-(alpha-hydroxyisovaleryl)-propionyl unit (HIP) and the protected amine of the n-butyl linker using a modification of Schmidt's protocol. After selective deprotection of the hydroxyl and amino groups of the macrocycle, the peptide side chain was introduced using (benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate (BOP) as the activating reagent.
• EWING, WILLIAM R.;HARRIS, BRUCE D.;LI, WEN-REN;JOULLIE, MADELEINE M., TETRAHEDRON LETT., 30,(1989) N9, C. 3757-3760
  作者：EWING, WILLIAM R.、HARRIS, BRUCE D.、LI, WEN-REN、JOULLIE, MADELEINE M.

  DOI：——

  日期：——