(3R,4R,5S,6S)-6-(tert-Butyl-dimethyl-silanyloxy)-2,4-dimethyl-hept-1-ene-3,5-diol | 491589-46-9

• 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: (3R,4R,5S,6S)-6-(tert-Butyl-dimethyl-silanyloxy)-2,4-dimethyl-hept-1-ene-3,5-diol
• CAS: 491589-46-9
• 化学式: C₁₅H₃₂O₃Si
• 分子量: 288.503
• InChiKey: DNQAFDQIMMMBGW-RFGFWPKPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.33
• 重原子数：
  19.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  49.69
• 氢给体数：
  2.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  2,2-二甲氧基丙烷 、 (3R,4R,5S,6S)-6-(tert-Butyl-dimethyl-silanyloxy)-2,4-dimethyl-hept-1-ene-3,5-diol 在 4-甲基苯磺酸吡啶 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Stereoselective synthesis of syn,syn-2-methyl-1,3-diols through one-pot aldol–reduction sequence

  摘要：

  Chx(2)BCl-inediated syn-aldol reaction of the alpha-OTBS lactate-derived ketone 1 followed by in situ reduction of the resulting boron aldolate with LiBH4 lead to complete stereoselectivity for the bororlates 2 in 80-95% yields. Then, a very mild oxidative work-up of 2 (H2O2/NaOAc in THF-H2O) allows isolation of syn,syn-2-methyl-1,3-diols 3 in yields up to 95% without migration of the TBS group. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)01289-3
• 作为产物：
  描述：

  3-戊酮,2-[[(1,1-二甲基乙基)二甲基甲硅烷基]氧代]-,(2S)- 在 双氧水 、 sodium acetate 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 水 为溶剂， 反应 7.0h， 生成 (3R,4R,5S,6S)-6-(tert-Butyl-dimethyl-silanyloxy)-2,4-dimethyl-hept-1-ene-3,5-diol
  参考文献：
  名称：

  Stereoselective synthesis of syn,syn-2-methyl-1,3-diols through one-pot aldol–reduction sequence

  摘要：

  Chx(2)BCl-inediated syn-aldol reaction of the alpha-OTBS lactate-derived ketone 1 followed by in situ reduction of the resulting boron aldolate with LiBH4 lead to complete stereoselectivity for the bororlates 2 in 80-95% yields. Then, a very mild oxidative work-up of 2 (H2O2/NaOAc in THF-H2O) allows isolation of syn,syn-2-methyl-1,3-diols 3 in yields up to 95% without migration of the TBS group. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)01289-3

文献信息

• Highly stereoselective titanium-mediated aldol reactions from chiral α-silyloxy ketones. A reliable tool for the synthesis of natural products
  作者：Judit Esteve、Carme Jiménez、Joaquim Nebot、Javier Velasco、Pedro Romea、Fèlix Urpí

  DOI：10.1016/j.tet.2011.06.019

  日期：2011.8

  Chiral α-silyloxy ketones participate in highly stereoselective TiCl4-mediated aldol reactions that afford diastereomerically pure syn–syn adducts in high yield irrespective of the R1 and R2 substituents flanking the carbonyl or the silicon protecting group. Further manipulation of the resulting aldol adducts provide in a straightforward manner highly functionalized fragments that facilitate the synthesis

  手性α-甲硅烷氧基酮参与高度立体选择性的TiCl 4介导的醛醇缩合反应，无论羰基或硅保护基旁的R 1和R 2取代基如何，都能以高收率获得非对映体纯的syn - syn加合物。所得醛醇加合物的进一步处理以直接的方式提供了高度官能化的片段，其促进了天然产物的合成。