triethyl-[[(2S,3S)-2-methyl-3-[(2R,3R)-3-triethylsilyloxyhexan-2-yl]oxiran-2-yl]methoxy]silane | 199284-28-1

• 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: triethyl-[[(2S,3S)-2-methyl-3-[(2R,3R)-3-triethylsilyloxyhexan-2-yl]oxiran-2-yl]methoxy]silane
• CAS: 199284-28-1
• 化学式: C₂₂H₄₈O₃Si₂
• 分子量: 416.792
• InChiKey: OEORVMYQISOKGQ-LRSLUSHPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.99
• 重原子数：
  27
• 可旋转键数：
  15
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  31
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  三乙基硅基三氟甲磺酸酯 、 triethyl-[[(2S,3S)-2-methyl-3-[(2R,3R)-3-triethylsilyloxyhexan-2-yl]oxiran-2-yl]methoxy]silane 在 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 120.0h， 以3%的产率得到(2R,3S,4S,5R)-2,4-Dimethyl-3,5-bis-triethylsilanyloxy-octanal
  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：

  (2S,3R)-3-(Triethylsilyloxy)-2-methylhexanal 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 lithium aluminium tetrahydride 、 N,N-二异丙基乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 144.0h， 生成 triethyl-[[(2S,3S)-2-methyl-3-[(2R,3R)-3-triethylsilyloxyhexan-2-yl]oxiran-2-yl]methoxy]silane
  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

• Use of Hindered Silyl Ethers as Protecting Groups for the Non-aldol Aldol Process
  作者：Michael E. Jung、Barbara Hoffmann、Bernhard Rausch、Jean-Marie Contreras

  DOI：10.1021/ol035295a

  日期：2003.8.1

  Bulky epoxy bis-silyl ethers, e.g., 15, derived from 5-trialkylsilyloxy-2-alken-1-ols by epoxidation and silylation were treated with TMSOTf to afford non-aldol aldol rearrangement products, the 3,5-bis(silyloxy)alkanals, e.g., 16, with little to none of the corresponding tetrahydrofurans.