(2S,3R)-3-(Triethylsilyloxy)-2-methylhexanal | 169944-44-9

• 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: (2S,3R)-3-(Triethylsilyloxy)-2-methylhexanal
• 英文别名: (2S,3R)-2-methyl-3-triethylsilyloxyhexanal
• CAS: 169944-44-9
• 化学式: C₁₃H₂₈O₂Si
• 分子量: 244.45
• InChiKey: OLBOOBTUSHADNS-CHWSQXEVSA-N

物化性质

• 沸点：
  273.2±23.0 °C(Predicted)
• 密度：
  0.862±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.01
• 重原子数：
  16
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 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)-3-(Triethylsilyloxy)-2-methylhexanal 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 lithium aluminium tetrahydride 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 143.0h， 生成 [(2S,3S)-2-methyl-3-[(2R,3R)-3-triethylsilyloxyhexan-2-yl]oxiran-2-yl]methanol
  参考文献：
  名称：

  Stereospecific Formation of Optically Active 5-Alkyl-4-methyl-3-[(trialkylsilyl)oxy]-2-([(trialkylsilyl)oxy]- methyl)tetrahydrofurans via Diastereoselective Epoxidation and Rearrangement of 5-[(Trialkylsilyl)oxy]-2-alken-1-ols¹

  摘要：

  A novel method for the synthesis of a series of silyl ethers of 3-(silyloxy)tetrahydrofuran-2-methanols bearing substituents at all four carbon atoms of the ring has been developed. The process involves first non-aldol aldol reaction of the epoxy silyl ether 8 to give the anti aldol product 9, stereoselective olefination and reduction to the (E)- and (Z)-allylic alcohols 10 and 11, diastereoselective epoxidation of these alcohols to give any of the four diastereomeric epoxy alcohols 12-15, silylation of the alcohols to give the epoxy silyl ethers 27-30, and final Lewis acid catalyzed rearrangement of the epoxy silyl ethers to give the desired products 31-33 and 36. In the first three instances, good yields of the desired 3-(silyloxy)-2-((silyloxy)methyl)tetrahydrofurans were obtained. However, rearrangement of the epoxy silyl ether 27 gave a mixture of products, the bis-silyl ether 36 as well as the products of a second non-aldol aldol process. This hydride migration to give the 3,5-bis((trialkylsilyl)oxy)-2,4-dimethylalkanal 35 or its internally protected 1-(silyloxy)pyran 38 can be made to occur in good yield.

  DOI：

  10.1021/ja972507o
• 作为产物：
  描述：

  三乙基硅基三氟甲磺酸酯 、 (2R,3R)-2,3-epoxy-2-methyl-1-hexanol 在 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以100%的产率得到(2S,3R)-3-(Triethylsilyloxy)-2-methylhexanal
  参考文献：
  名称：

  Stereospecific Formation of Optically Active 5-Alkyl-4-methyl-3-[(trialkylsilyl)oxy]-2-([(trialkylsilyl)oxy]- methyl)tetrahydrofurans via Diastereoselective Epoxidation and Rearrangement of 5-[(Trialkylsilyl)oxy]-2-alken-1-ols¹

  摘要：

  A novel method for the synthesis of a series of silyl ethers of 3-(silyloxy)tetrahydrofuran-2-methanols bearing substituents at all four carbon atoms of the ring has been developed. The process involves first non-aldol aldol reaction of the epoxy silyl ether 8 to give the anti aldol product 9, stereoselective olefination and reduction to the (E)- and (Z)-allylic alcohols 10 and 11, diastereoselective epoxidation of these alcohols to give any of the four diastereomeric epoxy alcohols 12-15, silylation of the alcohols to give the epoxy silyl ethers 27-30, and final Lewis acid catalyzed rearrangement of the epoxy silyl ethers to give the desired products 31-33 and 36. In the first three instances, good yields of the desired 3-(silyloxy)-2-((silyloxy)methyl)tetrahydrofurans were obtained. However, rearrangement of the epoxy silyl ether 27 gave a mixture of products, the bis-silyl ether 36 as well as the products of a second non-aldol aldol process. This hydride migration to give the 3,5-bis((trialkylsilyl)oxy)-2,4-dimethylalkanal 35 or its internally protected 1-(silyloxy)pyran 38 can be made to occur in good yield.

  DOI：

  10.1021/ja972507o

文献信息

• Stereospecific synthesis of aldols
  申请人：The Regents of the University of California

  公开号：US05426206A1

  公开（公告）日：1995-06-20

  Methods are provided for preparing all four diastereomers of 2-alkyl-3-hydroxyalkanals, 2-alkyl-3-silyloxyalkanals, and the like, with high enantiocontrol, using non-aldol chemistry. The synthetic methods also provide novel, stereospecific routes to polypropinates and chiral 2-substituted-1,3 diols.

  提供了一种方法，用于制备所有四种2-烷基-3-羟基烷醛、2-烷基-3-硅氧烷醛等的二对映异构体，具有高对映选择性，使用非醛缩合化学方法。合成方法还提供了新颖的、立体特异的聚丙烯酸酯和手性的2-取代-1,3-二醇的途径。
• Stereoselective production of β-amino alcohols and β-thioacyl alcohols via an application of the non-aldol aldol process
  作者：Michael E. Jung、Daqing Sun

  DOI：10.1016/s0040-4039(99)01786-4

  日期：1999.11

  The mesylates used as protecting groups to permit the formation of bis(polypropionates) via the nonaldol aldol process can be easily displaced with good nucleophiles, e.g., azide, thioacetate, acetate, to generate beta-azido (and beta-amino) alcohols, beta-thioacyl alcohols, and aldols of the opposite chirality, e.g.,syn isomers afford anti products. Thus the anti mesylate 15 affords the all-anti mzido aldol system 16 in good yield. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Synthesis of Four Diastereomeric 3,5-Dialkoxy-2,4-dimethylalkanals by a Simple Extension of the Non-Aldol Aldol Process to Bis(propionates)
  作者：Michael E. Jung、Woo Song Lee、Daqing Sun

  DOI：10.1021/ol990619+

  日期：1999.7.1

  [GRAPHICS]The synthesis of all four diastereomers of bis(propionates), 3,5-dialkoxy-2,4-dimethylalkanals, by non-aldol aldol chemistry is described. The epoxy alcohols (3, 4) were converted into the mesylates (9, 11) which were cleanly rearranged to the desired 3,5-bis(oxygenated)-2,4 dimethylalkanals (10, 12) in high yield. The epoxy mesylates (13, 16) gave the desired products (14, 17) in good yield on treatment with TMSOTf and a hindered base.