(2S,4R,5R)-2-tert-butyldimethylsilyloxy-5-hydroxy-4,6-dimethyl-6-hepten-3-one | 188677-77-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,4R,5R)-2-tert-butyldimethylsilyloxy-5-hydroxy-4,6-dimethyl-6-hepten-3-one
• 英文别名: (2S,4R,5R)-2-[tert-butyl(dimethyl)silyl]oxy-5-hydroxy-4,6-dimethylhept-6-en-3-one
• CAS: 188677-77-2
• 化学式: C₁₅H₃₀O₃Si
• 分子量: 286.487
• InChiKey: STAAEUMKGXMIFE-AGIUHOORSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.54
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,4R,5R)-2-tert-butyldimethylsilyloxy-5-hydroxy-4,6-dimethyl-6-hepten-3-one 在 2,6-二甲基吡啶 、 camphor-10-sulfonic acid 、 二异丁基氢化铝 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 19.58h， 生成 (2S,3S,4S,5R)-4,6-dimethyl-2-triethylsilyloxy-5-tri(propan-2-yl)silyloxyhept-6-en-3-ol
  参考文献：
  名称：

  研究方向为肉毒杆菌素的总合成，肉毒杆菌内酯的修订结构：高度取代的四氢吡喃部分的合成

  摘要：

  合成了高取代度的植物酸多氧合四氢吡喃环，通过使用乳酸酯衍生的手性酮的烯醇钛的高度立体选择性醛醇缩合反应和立体选择性二羟基化反应作为关键步骤，实现了肉毒杆菌酯的修饰结构。

  DOI：

  10.1016/j.tetlet.2007.07.068
• 作为产物：
  描述：

  (S)-2-(tert-butyldimethylsilanyloxy)-N-methoxy-N-methylpropionamide 在 四氯化钛 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 (2S,4R,5R)-2-tert-butyldimethylsilyloxy-5-hydroxy-4,6-dimethyl-6-hepten-3-one
  参考文献：
  名称：

  Stereoselective titanium-mediated aldol reactions of (S)-2-tert-butyldimethylsilyloxy-3-pentanone

  摘要：

  Titanium-mediated aldol reactions based on (S)-2-tert-butyldimethylsilyloxy-3-pentanone, a lactate-derived chiral ketone, provide the corresponding 2,4-syn-4,5-syn adducts in high yields and diastereomeric ratios with a wide array of achiral and chiral aldehydes. Furthermore, spectroscopic studies of intermediates involved in the process have permitted to propose a mechanism that accounts for the experimental results. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.09.034

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。
• Highly stereoselective aldol reactions of titanium enolates from ethyl α-silyloxyalkyl ketones
  作者：Sergi Figueras、Ricardo Martín、Pedro Romea、Fèlix Urpí、Jaume Vilarrasa

  DOI：10.1016/s0040-4039(97)00108-1

  日期：1997.3

  Aldol-like reactions of titanium enolates derived from α-OH, α-OBn, and α-OTBS ketones with a series of aldehydes have been studied. In sharp contrast to the O-benzyl derivatives, the TBS-protected ketones lead to excellent yields and selectivities ( ratios from 30:1 to >95:1) even for the lactate-derived substrate (2-tert-butyldimethylsilyloxy-3-pentanone).

  研究了衍生自α-OH，α-OBn和α-OTBS酮的烯醇钛酸酯与一系列醛类的醛醇缩合反应。与O-苄基衍生物形成鲜明对比的是，即使对于乳酸衍生的底物（2-叔丁基二甲基甲硅烷氧基-3-戊酮），TBS保护的酮也可产生出色的收率和选择性（比率从30：1到> 95：1）。）。
• Stereoselective titanium-mediated aldol reactions of (S)-2-tert-butyldimethylsilyloxy-3-pentanone
  作者：Joaquim Nebot、Sergi Figueras、Pedro Romea、Fèlix Urpí、Yining Ji

  DOI：10.1016/j.tet.2006.09.034

  日期：2006.11

  Titanium-mediated aldol reactions based on (S)-2-tert-butyldimethylsilyloxy-3-pentanone, a lactate-derived chiral ketone, provide the corresponding 2,4-syn-4,5-syn adducts in high yields and diastereomeric ratios with a wide array of achiral and chiral aldehydes. Furthermore, spectroscopic studies of intermediates involved in the process have permitted to propose a mechanism that accounts for the experimental results. (c) 2006 Elsevier Ltd. All rights reserved.
• Studies directed towards the total synthesis of botcinic acid, the revised structure of botcinolide: synthesis of the highly substituted tetrahydropyran moiety
  作者：Tushar Kanti Chakraborty、Rajib Kumar Goswami

  DOI：10.1016/j.tetlet.2007.07.068

  日期：2007.9

  Synthesis of the highly substituted polyoxygenated tetrahydropyran ring of botcinic acid, the revised structure of botcinolide is achieved using, as key steps, a highly stereoselective aldol reaction of the titanium enolate from a lactate-derived chiral ketone and a stereoselective dihydroxylation.

  合成了高取代度的植物酸多氧合四氢吡喃环，通过使用乳酸酯衍生的手性酮的烯醇钛的高度立体选择性醛醇缩合反应和立体选择性二羟基化反应作为关键步骤，实现了肉毒杆菌酯的修饰结构。