(1R,2R,4S)-4-tert-butyldimethylsilyloxy-1-hydroxy-2-methyl-1-phenyl-3-pentanone | 188677-78-3

• 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: (1R,2R,4S)-4-tert-butyldimethylsilyloxy-1-hydroxy-2-methyl-1-phenyl-3-pentanone
• 英文别名: (1R,2R,4S)-4-[tert-butyl(dimethyl)silyl]oxy-1-hydroxy-2-methyl-1-phenylpentan-3-one
• CAS: 188677-78-3
• 化学式: C₁₈H₃₀O₃Si
• 分子量: 322.52
• InChiKey: ILJOFIMWLBUQIZ-GRDNDAEWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.34
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 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：

  (1R,2R,4S)-4-tert-butyldimethylsilyloxy-1-hydroxy-2-methyl-1-phenyl-3-pentanone 在 sodium periodate 、 氢氟酸 作用下， 以 甲醇 、 水 、 乙腈 为溶剂， 反应 3.25h， 生成 (2R,3R)-(+)-3-hydroxy-2-methyl-3-phenylpropanoic acid
  参考文献：
  名称：

  用二环己基氯硼烷烯化手性α-甲硅烷氧基酮。应用于立体选择性醛醇缩合反应

  摘要：

  [反应：参见文本] Chx2BCl / R3N对α-甲硅烷基氧酮烯醇化的全面分析，使我们能够设计立体选择性Chx2BCl介导的羟醛工艺，该工艺提供顺式或反式羟醛产物，并揭示一种假说，该假说解释了确定他们的烯醇化。

  DOI：

  10.1021/ol006109t
• 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 (1R,2R,4S)-4-tert-butyldimethylsilyloxy-1-hydroxy-2-methyl-1-phenyl-3-pentanone
  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

• Enolization of Chiral α-Silyloxy Ketones with Dicyclohexylchloroborane. Application to Stereoselective Aldol Reactions
  作者：Marta Galobardes、Miguel Gascón、Marisa Mena、Pedro Romea、Fèlix Urpí、Jaume Vilarrasa

  DOI：10.1021/ol006109t

  日期：2000.8.1

  [reaction: see text]Comprehensive analysis of the enolization of alpha-silyloxyketones by Chx2BCl/R3N has allowed us to design stereoselective Chx2BCl-mediated aldol processes that afford syn or anti aldol products and to disclose a hypothesis that accounts for the subtle effects that determine their enolization.

  [反应：参见文本] Chx2BCl / R3N对α-甲硅烷基氧酮烯醇化的全面分析，使我们能够设计立体选择性Chx2BCl介导的羟醛工艺，该工艺提供顺式或反式羟醛产物，并揭示一种假说，该假说解释了确定他们的烯醇化。
• Highly Diastereoselective Aldol Additions of a Chiral Ethyl Ketone Enolate under Lewis Base Catalysis
  作者：Scott E. Denmark、Son M. Pham

  DOI：10.1021/ol0160497

  日期：2001.7.1

  [reaction: see text] The aldol addition of a chiral ethyl ketone enolate bearing an oxygen substituent (OTBS) at the alpha-position proceeds with high internal and relative diastereoselectivities with various achiral aldehydes in good yields. The profound influence of the resident stereogenic center allows for the use of an achiral catalyst, such as HMPA, with minor attenuation in internal stereoselectivity

  [反应：见正文]在α-位上带有氧取代基（OTBS）的手性乙基酮烯醇式醛醇醛的加成反应具有高的内部和相对非对映选择性以及各种非手性醛的收率。驻留立体中心的深远影响允许使用非手性催化剂，例如HMPA，内部立体选择性的衰减较小。
• 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.