(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 | 130008-94-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (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
• 英文别名: [(3S,4S,5R)-6-[tert-butyl(dimethyl)silyl]oxy-4-(methoxymethoxy)-2,5-dimethylhexan-3-yl] (3R,4R,5S)-5-methyl-4-(phenylmethoxycarbonylamino)-3-tri(propan-2-yl)silyloxyheptanoate
• CAS: 130008-94-5
• 化学式: C₄₁H₇₇NO₈Si₂
• 分子量: 768.235
• InChiKey: CZFVZPFUGSIFGT-NPPJUVOISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.49
• 重原子数：
  52
• 可旋转键数：
  26
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  102
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  L-缬氨酸 在 硫酸 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 钾硼氢 、 pyridine-SO3 complex 、 三氟甲磺酸 、 硫酸 、 氨 、 sodium 、 四氯化锡 、 二甲基亚砜 、 三乙胺 、 N,N-二异丙基乙胺 、 lithium diisopropyl amide 、 sodium nitrite 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 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

文献信息

• Total synthesis and structural investigations of didemnins A, B, and C
  作者：Wen Ren Li、William R. Ewing、Bruce D. Harris、Madeleine M. Joullie

  DOI：10.1021/ja00177a030

  日期：1990.10

  Didemnins A, B, and C were efficiently prepared in a stereocontrolled manner, producing the common macrocycle and, in a separate step, introducing the substituents on the amino group of L-threonine as optically pure units. We envisaged that disconnections between L-leucine and the HIP group (2S,4S) and between L-threonine and isostatine (3S,4R,5S) would afford two units: a HIP-isostatine unit (I) and

  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) )
• 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.