(2S,4R,5R)-2-benzyloxy-5-hydroxy-4,6-dimethyl-6-hepten-3-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,4R,5R)-2-benzyloxy-5-hydroxy-4,6-dimethyl-6-hepten-3-one
• 英文别名: (2S,4R,5R)-5-hydroxy-4,6-dimethyl-2-phenylmethoxyhept-6-en-3-one
• 化学式: C₁₆H₂₂O₃
• 分子量: 262.349
• InChiKey: YKKYTMJLRLZLQF-IPYPFGDCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  19
• 可旋转键数：
  7
• 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：

  (S)-2-(benzyloxy)-N-methoxy-N-methylpropanamide 在 氯代二环己基硼烷 、 双氧水 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 19.0h， 生成 (2S,4R,5R)-2-benzyloxy-5-hydroxy-4,6-dimethyl-6-hepten-3-one
  参考文献：
  名称：

  Studies in polypropionate synthesis: High π-face selectivity in syn and anti aldol reactions of chiral boron enolates of lactate-derived ketones

  摘要：

  Use of (c)Hex(2)BCl/Me(2)NEt in the aldol reactions of the alpha'-benzoyloxy ketone 7 with aldehydes leads to high stereoselectivity (97-99.5% ds) for the crystalline anti adducts 11. Under similar conditions, the corresponding benzyl ether 6 favours formation of the syn adducts 9.

  DOI：

  10.1016/0040-4039(94)88434-x

文献信息

• Highly Stereoselective Aldol Reactions of Titanium Enolates from Lactate-Derived Chiral Ketones
  作者：Joan G. Solsona、Pedro Romea、Fèlix Urpí、Jaume Vilarrasa

  DOI：10.1021/ol0274054

  日期：2003.2.1

  [reaction: see text] Highly stereoselective titanium-mediated aldol reactions based on lactate-derived ketones are reported. The stereochemical outcome of the process depends on the protecting group (PMB or Bn) and the Lewis acid (i-PrOTiCl(3) or TiCl(4)) used in the enolization step, the corresponding anti-syn or syn-syn aldols being prepared in high yields and with diastereomeric ratios up to 99:1

  [反应：见正文]据报道，基于乳酸衍生的酮具有高度立体选择性的钛介导的羟醛反应。该方法的立体化学结果取决于烯醇化步骤中使用的保护基（PMB或Bn）和路易斯酸（i-PrOTiCl（3）或TiCl（4）），相应的反-syn或syn-syn-醛醇为以高收率和高达99：1的非对映异构体比例制备。
• Stereoselective titanium-mediated syn -aldol reaction from a lactate-derived chiral ethyl ketone
  作者：Joan G Solsona、Pedro Romea、Fèlix Urpı́

  DOI：10.1016/j.tetlet.2004.05.077

  日期：2004.7

  TiCl4 has given access to the corresponding 2,4-anti-4,5-syn aldol adducts with the highest diastereomeric ratios. The excellent stereocontrol exerted by the aforementioned ketone has been demonstrated in double asymmetric reactions involving chiral α-methyl-β-OTBDPS aldehydes.

  路易斯酸的存在极大地改变了基于（S）-2-苄氧基-3-戊酮1的钛介导的羟醛工艺的立体选择性。在所调查的路易斯酸中，TiCl 4获得了具有最高非对映异构体比例的相应2,4-抗-4,5-顺式羟醛加成物。在涉及手性α-甲基-β-OTBDPS醛的双不对称反应中，已经证明了上述酮发挥的优异的立体控制作用。
• Highly Stereoselective TiCl₄-Mediated Aldol Reactions from (<i>S</i>)-2-Benzyloxy-3-pentanone
  作者：Victor Rodríguez-Cisterna、Cristina Villar、Pedro Romea、Fèlix Urpí

  DOI：10.1021/jo071048z

  日期：2007.8.1

  Stereoselectivity of TiCl4-mediated aldol reactions from (S)-2-benzyloxy-3-pentanone is dramatically improved when the reaction is carried out in the presence of 1.1 equiv of tetrahydrofuran (THF) or 1,2-dimethoxyethane (DME). The resultant 2,4-syn-4,5-syn adducts are then obtained in diastereomeric ratios up to 97:3, which proves that the appropriate choice of the Lewis acid (TiCl4−THF or DME vs Ti(i-PrO)Cl3)

  当在1.1当量的四氢呋喃（THF）或1,2-二甲氧基乙烷（DME）的存在下进行反应时，由（S）-2-苄氧基-3-戊酮进行的TiCl 4介导的羟醛反应的立体选择性大大提高。将所得的2,4-顺式-4,5-顺式加合物然后在非对映体比例高达获得至97:3，这证明了路易斯酸的适当选择（的TiCl 4 -THF或DME VS的Ti（我-Pro）参与该过程的Cl 3）允许同时获得两个顺式-羟醛加合物。
• Studies in polypropionate synthesis: High π-face selectivity in syn and anti aldol reactions of chiral boron enolates of lactate-derived ketones
  作者：Ian Paterson、Debra J. Wallace、Silvia M. Velázquez

  DOI：10.1016/0040-4039(94)88434-x

  日期：1994.11

  Use of (c)Hex(2)BCl/Me(2)NEt in the aldol reactions of the alpha'-benzoyloxy ketone 7 with aldehydes leads to high stereoselectivity (97-99.5% ds) for the crystalline anti adducts 11. Under similar conditions, the corresponding benzyl ether 6 favours formation of the syn adducts 9.