(2S,3S)-(E)-tert-butyl 3-hydroxy-2-methyl-5-phenylpent-4-enoate | 127422-15-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: (2S,3S)-(E)-tert-butyl 3-hydroxy-2-methyl-5-phenylpent-4-enoate
• 英文别名: tert-butyl (2S,3S,4E)-3-hydroxy-2-methyl-5-phenylpent-4-enoate；(2S,3S) tert-butyl 3-hydroxy-2-methyl-5-phenyl-4-pentenoate；tert-butyl (2S,3S)-3-hydroxy-2-methyl-5-phenyl-4-pentenoate；tert-butyl (E,2S,3S)-3-hydroxy-2-methyl-5-phenylpent-4-enoate
• CAS: 127422-15-5
• 化学式: C₁₆H₂₂O₃
• 分子量: 262.349
• InChiKey: GTOHDUXJKMINIV-IWYIRLTCSA-N

物化性质

• 熔点：
  80-82 °C
• 沸点：
  200 °C(Press: 0.01 Torr)
• 密度：
  1.058±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  反式肉桂醛 、 [(1-tert-butyloxy)propenyloxy]-tert-butyldimethylsilane 在 四氯化硅 、 (R,R)-N,N'-bis(phosphoramide)-N,N'-Me₂-1,5-pentanediamine 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以98%的产率得到(2S,3S)-(E)-tert-butyl 3-hydroxy-2-methyl-5-phenylpent-4-enoate
  参考文献：
  名称：

  路易斯酸的路易斯碱活化：甲硅烷基乙烯酮缩醛催化、对映选择性加成到醛

  摘要：

  路易斯酸的路易斯碱活化的概念已被简化用于催化甲硅烷基乙烯酮缩醛和甲硅烷基二烯醇醚与醛的羟醛反应。弱酸性物质四氯化硅 (SiCl4) 可以通过结合强路易斯碱性手性磷酰胺而被激活，导致手性路易斯酸的原位形成。该物质已被证明是将乙酸酯、丙酸酯和异丁酸酯衍生的甲硅烷基乙烯酮缩醛与共轭和非共轭醛进行羟醛加成反应的有效催化剂。此外，还证明了甲硅烷基二烯醇醚的乙烯基羟醛反应。高水平的区域-，抗非对映-，

  DOI：

  10.1021/ja047339w

文献信息

• High Performance of Rh(Phebox) Catalysts in Asymmetric Reductive Aldol Reaction:  High Anti-Selectivity
  作者：Hisao Nishiyama、Takushi Shiomi、Yasunori Tsuchiya、Isamu Matsuda

  DOI：10.1021/ja050698m

  日期：2005.5.1

  Chiral rhodium(bisoxazolinylphenyl) complexes (1 mol %) efficiently catalyze the asymmetric reductive aldol reaction of aldehydes and alpha,beta-unsaturated esters at 50 degrees C for ca. 0.5-1.0 h with several hydrosilanes to give the corresponding beta-hydroxypropionates with extremely high anti-selectivity (up to 98%) and enantioselectivity (up to 96% ee). The stereochemical outcome is likely due

  手性铑(双恶唑啉基苯基) 配合物 (1 mol %) 有效地催化醛和 α，β-不饱和酯在 50 摄氏度的不对称还原醛醇反应约。使用几种氢硅烷反应 0.5-1.0 小时，得到具有极高抗选择性（高达 98%）和对映选择性（高达 96% ee）的相应 β-羟基丙酸酯。立体化学结果可能是由于涉及铑-(E)-烯醇化物的椅子状循环过渡态。
• Lewis Base Activation of Lewis Acids. Addition of Silyl Ketene Acetals to Aldehydes
  作者：Scott E. Denmark、Thomas Wynn、Gregory L. Beutner

  DOI：10.1021/ja0282947

  日期：2002.11.1

  olefinic aldehydes as well as aliphatic aldehydes (albeit more slowly) with excellent enantioselectivity. The homologous tert-butyldimethylsilyl ketene acetal of tert-butyl propanoate adds with nearly exclusive anti diastereoselectivity to a similar range of aldehydes also with excellent enantioselectivity. The origin of the slower reaction rate with aliphatic aldehydes is revealed to be the formation of chlorosilyl

  弱路易斯酸四氯化硅可以被催化量的手性双磷酰胺 (R,R)-3 活化，形成高反应性的手性三氯甲硅烷基阳离子，它是醛和甲硅烷基乙烯酮缩醛之间羟醛加成反应的极其有效的促进剂。乙酸甲酯的叔丁基二甲基甲硅烷基乙烯酮缩醛几乎立即添加到芳香族和烯烃醛以及脂肪族醛中（尽管速度更慢），具有出色的对映选择性。丙酸叔丁酯的同源叔丁基二甲基甲硅烷基乙烯酮缩醛为类似范围的醛类添加了几乎独有的抗非对映选择性，同时也具有出色的对映选择性。与脂肪醛反应速度较慢的原因是氯甲硅烷基醚加合物的形成。
• New process for enantioselective nucleophilic addition to aldehydes to form secondary alcohols
  作者：E.J. Corey、Sung Soo Kim

  DOI：10.1016/s0040-4039(00)97452-5

  日期：——

  New methodology is described for the enantioselective conversion of aldehydes to anti aldols 4 and homoallylic alcohols 7.

  新的方法是为醛以对映选择性转换描述抗醛醇4和高烯丙基醇7。
• (Diisopinocampheyl)borane-Mediated Reductive Aldol Reactions of Acrylate Esters: Enantioselective Synthesis of <i>Anti</i>-Aldols
  作者：Christophe Allais、Philippe Nuhant、William R. Roush

  DOI：10.1021/ol401679g

  日期：2013.8.2

  The (diisopinocampheyl)borane promoted reductive aldol reaction of acrylate esters 4 is described. Isomerization of the kinetically formed Z(O)-enolborinate 5Z to the thermodynamic E(O)-enolborinate 5E via 1,3-boratropic shifts, followed by treatment with representative achiral aldehydes, leads to anti-alpha-methyl-beta-hydroxy esters 9 or 10 with excellent diastereo- (up to >= 20:1 dr) and enantioselectivity (up to 87% ee). The results of double asymmetric reactions of 5E with several chiral aldehydes are also presented.
• Asymmetric Aldol Reaction with Diisopinocampheyl Enolborinates of Propionates
  作者：P. Veeraraghavan Ramachandran、Debarshi Pratihar

  DOI：10.1021/ol802850w

  日期：2009.4.2

  A convenient and general, reagent-controlled, diastereo- and enantioselective aldol reaction of diisopinocampheylboron enolates of esters, followed by reduction, has been developed as an alternative to crotylboration-ozonolysis. This protocol was then exploited for the double diastereoselective synthesis of the C11-C17 subunit of (-)-dictyostatin.