methyl (2S,3R)-α-azido-β-(dimethylphenylsilyl)-(E)-hex-4-enoate | 136824-21-0

• 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: methyl (2S,3R)-α-azido-β-(dimethylphenylsilyl)-(E)-hex-4-enoate
• 英文别名: (2S,3R)-Methyl 2-azido-3-(dimethylphenylsilyl)-(E)-hex-4-enoate；(2S,3R)-Methyl 2-azido-3-(dimethylphenylsilyl)hex-4-enoate；methyl (E,2S,3R)-2-azido-3-[dimethyl(phenyl)silyl]hex-4-enoate
• CAS: 136824-21-0
• 化学式: C₁₅H₂₁N₃O₂Si
• 分子量: 303.436
• InChiKey: IVYGGYULHXTPKQ-KEGUIYOVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  40.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (2S,3R)-α-azido-β-(dimethylphenylsilyl)-(E)-hex-4-enoate 在 盐酸 作用下， 以 乙醚 为溶剂， 生成 methyl (E,2S,3R)-2-amino-3-[dimethyl(phenyl)silyl]hex-4-enoate
  参考文献：
  名称：

  Diastereoselectivity in the osmium tetraoxide promoted dihydroxylation of chiral (E)-crotylsilane: asymmetric synthesis of silyl-functionalized .gamma.-lactones

  摘要：

  The catalytic osmylation of enantiomerically enriched (E)-crotylsilanes (2S,3R)-1 and (2R,3R)-2 containing a homoallylic, nitrogen-bearing stereocenter proceeds with good to high levels of diastereoselection generating silyl-functionalized trans-4,5 substituted gamma-lactones 3 and 5 as the major diastereomers.

  DOI：

  10.1021/jo00054a002
• 作为产物：
  描述：

  4-己烯酸,3-(二甲基苯基甲硅烷基)-,甲基酯,(3S,4E)- 在 正丁基锂 、 2,4,6-三异丙基苯磺酰叠氮化物 、 溶剂黄146 、 二异丙胺 作用下， 生成 methyl (2R,3R)-α-azido-β-(dimethylphenylsilyl)-(E)-hex-4-enoate 、 methyl (2S,3R)-α-azido-β-(dimethylphenylsilyl)-(E)-hex-4-enoate
  参考文献：
  名称：

  Diastereoselective electrophilic addition reactions to chiral .beta.-dimethylphenylsilyl ester enolates. Synthesis of 2,3-anti-.alpha.-substituted-.beta.-silyl-(E)-hex-4-enoates

  摘要：

  DOI：

  10.1021/jo00026a030

文献信息

• Enantioselective Synthesis of the Protein Phosphatase Inhibitor (−)-Motuporin
  作者：Tao Hu、James S. Panek

  DOI：10.1021/ja0206700

  日期：2002.9.1

  A highly convergent asymmetric synthesis of the protein phosphatase inhibitor motuporin 1a is described. Synthesis and coupling of the individual peptide fragments [34 + 35 --> 51] followed by macrocyclization afforded the fully protected motuporin precursor 33, which is converted to the natural product by dehydration and ester hydrolysis. Six of the eight stereogenic centers associated with the natural

  描述了蛋白质磷酸酶抑制剂 motuporin 1a 的高度收敛不对称合成。单个肽片段 [34 + 35 --> 51] 的合成和偶联，然后进行大环化，得到完全保护的 motuporin 前体 33，通过脱水和酯水解将其转化为天然产物。使用不对称巴豆基硅烷键构建方法引入与天然产物相关的八个立体中心中的六个。我们的方法的特点是在构型明确的乙烯基锌中间体 22 和 (E)-乙烯基碘化物 7 之间进行有效的 Pd(0) 催化交叉偶联反应，得到化合物 43，从而构建了三取代的 (E, E)-motuporin 侧链的二烯系统。
• Asymmetric Synthesis of (2<i>S</i>,3<i>S</i>,8<i>S</i>,9<i>S</i>)-<i>N</i>-Boc ADDA:  Application of a Palladium(0)-Catalyzed Cross-Coupling Reaction of Trisubstituted Olefins
  作者：James S. Panek、Tao Hu

  DOI：10.1021/jo9706483

  日期：1997.7.1
• Sequential diastereoselective addition and allylic azide isomerization of syn- and anti-.alpha.-azido-.beta.-(dimethylphenylsilyl)-(E)-hex-4-enoates with acetals: asymmetric synthesis of .gamma.-hydroxy-.alpha.-amino acid synthons
  作者：James S. Panek、Michael Yang、Itzhak Muler

  DOI：10.1021/jo00041a002

  日期：1992.7

  syn- and anti-methyl alpha-azido-beta-(dimethylphenylsilyl)-(E)-hex-4-enoates (2R,3R)-1a and (2S,3R)-1b undergo highly diastereo- and enantioselective addition reactions with oxonium ions catalyzed by the action of trimethylsilyl trifluoromethanesulfonate (TMSOTf) to generate alpha-azido-beta,gamma-unsaturated esters 2, with well-defined 1,4- and 1,5-stereochemical relationships, and a subsequent stereospecific allylic azide isomerization generated 1,3-azido ethers 3, synthetic equivalents of gamma-hydroxy-alpha-amino acids.