<2S,3R>-2-methyl-3-(triethylsiloxy)-4-pentenal | 131698-83-4

• 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: <2S,3R>-2-methyl-3-(triethylsiloxy)-4-pentenal
• 英文别名: (2S,3R)-2-methyl-3-triethylsilyloxypent-4-enal
• CAS: 131698-83-4
• 化学式: C₁₂H₂₄O₂Si
• 分子量: 228.407
• InChiKey: STODLCLEYOAXAN-VXGBXAGGSA-N

物化性质

• 沸点：
  264.7±28.0 °C(predicted)
• 密度：
  0.872±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  15
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  <2S,3R>-2-methyl-3-(triethylsiloxy)-4-pentenal 在 2,6-二甲基吡啶 、 9-borabicyclo[3.3.1]nonane dimer 、 三氟化硼乙醚 、 氢氟酸 、 双氧水 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 26.0h， 生成 2,2-Dimethyl-propionic acid (R)-3-[(2S,3S,5S,7R,8S,9S)-9-(tert-butyl-dimethyl-silanyloxy)-7-[2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-3-(4-methoxy-benzyloxy)-4,4,8-trimethyl-1,6-dioxa-spiro[4.5]dec-2-yl]-3-methoxy-propyl ester
  参考文献：
  名称：

  Total synthesis of (+)-calyculin A

  摘要：

  A convergent asymmetric synthesis of the marine natural product calyculin A has been accomplished through the union of the two subunits comprising the C1-C25 and C26-C37 portions of the molecule. These fragments were constructed utilizing auxiliary-based asymmetric aldol, alkylation, hydroxylation, and Michael reactions to establish 10 of the 15 stereogenic centers, The remaining chirality was incorporated through internal asymmetric induction. Stereoselective Wittig coupling of the two fragments and subsequent deprotection provided synthetic calyculin A. The spectral properties of the synthetic material were in complete agreement with those of the natural material except for the optical rotation which was equal and opposite in sign to that of the natural material. The absolute configuration of (-)-calyculin A has thus been shown to be opposite to that illustrated in structure 1.

  DOI：

  10.1021/ja00050a024
• 作为产物：
  描述：

  <4S,3(2S,3R)>-4-benzyl-3-(3-hydroxy-2-methyl-4-pentenoyl)-2-oxazolidinone 在 三甲基铝 、 二异丁基氢化铝 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 生成 <2S,3R>-2-methyl-3-(triethylsiloxy)-4-pentenal
  参考文献：
  名称：

  Total synthesis of (+)-calyculin A

  摘要：

  A convergent asymmetric synthesis of the marine natural product calyculin A has been accomplished through the union of the two subunits comprising the C1-C25 and C26-C37 portions of the molecule. These fragments were constructed utilizing auxiliary-based asymmetric aldol, alkylation, hydroxylation, and Michael reactions to establish 10 of the 15 stereogenic centers, The remaining chirality was incorporated through internal asymmetric induction. Stereoselective Wittig coupling of the two fragments and subsequent deprotection provided synthetic calyculin A. The spectral properties of the synthetic material were in complete agreement with those of the natural material except for the optical rotation which was equal and opposite in sign to that of the natural material. The absolute configuration of (-)-calyculin A has thus been shown to be opposite to that illustrated in structure 1.

  DOI：

  10.1021/ja00050a024

文献信息

• Reversal of aldehyde diastereofacial selectivity in a methyl ketone aldol reaction. Application to the synthesis of the calyculin spiroketal
  作者：David A. Evans、James R. Gage

  DOI：10.1016/s0040-4039(00)97005-9

  日期：1990.1

  It has been observed that aldehyde diastereofacial selectivity in a methyl ketone aldol reaction can be fully regulated under appropriate conditions. Addition of the lithium enolate provided the product derived from apparent chelation control, while Lewis acid-promoted addition of the derived silyl enol ether afforded the Felkin-Anh diastereomer. Application of this methodology to the ongoing synthesis

  业已发现，在适当的条件下，可以完全调节甲基酮醛醇缩醛反应中的醛非对映选择性。加入烯酸锂提供了从明显的螯合控制得到的产物，而路易斯酸促进的得到的甲硅烷基烯醇醚的加入得到了Felkin-Anh非对映异构体。提出了该方法在正在进行的凯里素A合成中的应用。
• Asymmetric synthesis of calyculin A. 1. The C1-C25 spiroketal fragment
  作者：David A. Evans、James R. Gage

  DOI：10.1021/jo00033a009

  日期：1992.3

  An asymmetric synthesis of the C1-C25 portion of calyculin A has been developed.
• EVANS, DAVID A.;GAGE, JAMES R., TETRAHEDRON LETT., 31,(1990) N3, C. 6129-6132
  作者：EVANS, DAVID A.、GAGE, JAMES R.

  DOI：——

  日期：——