(Z)-methyl-1-(tert-butyldimethylsilyloxy)-2-methyl-4-butenoate | 257612-05-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (Z)-methyl-1-(tert-butyldimethylsilyloxy)-2-methyl-4-butenoate
• 英文别名: methyl (Z)-4-((tert-butyldimethylsilyl)oxy)-3-methylbut-2-enoate；methyl (Z)-4-[tert-butyl(dimethyl)silyl]oxy-3-methylbut-2-enoate
• CAS: 257612-05-8
• 化学式: C₁₂H₂₄O₃Si
• 分子量: 244.406
• InChiKey: HTJIGOGNVJJPBH-NTMALXAHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.13
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (Z)-methyl-1-(tert-butyldimethylsilyloxy)-2-methyl-4-butenoate 在 4-二甲氨基吡啶 、 二异丁基氢化铝 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 生成 dimethyl 1-(tert-butyldimethylsilyloxy)-2-methyl-buten-4-phosphate
  参考文献：
  名称：

  Synthesis of 2-C-Methyl-d-erythritol 4-Phosphate:  The First Pathway-Specific Intermediate in the Methylerythritol Phosphate Route to Isoprenoids

  摘要：

  2-C-Methyl-D-erythritol 4-phosphate (4), formed from 1-deoxy-D-xylulose 5-phosphate (3), is the first pathway-specific intermediate in the methylerythritol phosphate route for the biosynthesis of isoprenoid compounds in bacteria, algae, and plant chloroplasts. In this report, 4 was synthesized from 1,2 propanediol (7) in seven steps with an overall yield of 32% and in an enantiomeric excess of 78%.

  DOI：

  10.1021/ol991299x
• 作为产物：
  描述：

  叔丁基二甲基(2-丙炔氧基)硅烷 在 正丁基锂 、 copper bromide dimethyl sulfide complex 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 生成 (Z)-methyl-1-(tert-butyldimethylsilyloxy)-2-methyl-4-butenoate
  参考文献：
  名称：

  Synthesis of 2-C-Methyl-d-erythritol 4-Phosphate:  The First Pathway-Specific Intermediate in the Methylerythritol Phosphate Route to Isoprenoids

  摘要：

  2-C-Methyl-D-erythritol 4-phosphate (4), formed from 1-deoxy-D-xylulose 5-phosphate (3), is the first pathway-specific intermediate in the methylerythritol phosphate route for the biosynthesis of isoprenoid compounds in bacteria, algae, and plant chloroplasts. In this report, 4 was synthesized from 1,2 propanediol (7) in seven steps with an overall yield of 32% and in an enantiomeric excess of 78%.

  DOI：

  10.1021/ol991299x

文献信息

• Bond-Weakening Catalysis: Conjugate Aminations Enabled by the Soft Homolysis of Strong N–H Bonds
  作者：Kyle T. Tarantino、David C. Miller、Ted A. Callon、Robert R. Knowles

  DOI：10.1021/jacs.5b03428

  日期：2015.5.27

  The ability of redox-active metal centers to weaken the bonds in associated ligands is well precedented, but has rarely been utilized as a mechanism of substrate activation in catalysis. Here we,describe a catalytic bond-weakening protocol for conjugate amination wherein the strong N-H bonds in N-aryl amides (N-H bond dissociation free energies similar to 100 kcal/mol) are destabilized by similar to 33 kcal/mol upon by coordination to a reducing titanocene complex, enabling their abstraction by the weak H-atom acceptor TEMPO through a proton-coupled electron transfer process. Significantly, this soft homolysis mechanism provides a method to generate closed-shell, metalated nucleophiles under neutral conditions in the absence of a Bronsted base.