(2R,3R)-2-Methyl-3-((1R,2R)-1-methyl-2-triethylsilanyloxy-pentyl)-2-triethylsilanyloxymethyl-oxirane | 199284-29-2

• 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: (2R,3R)-2-Methyl-3-((1R,2R)-1-methyl-2-triethylsilanyloxy-pentyl)-2-triethylsilanyloxymethyl-oxirane
• 英文别名: triethyl-[[(2R,3R)-2-methyl-3-[(2R,3R)-3-triethylsilyloxyhexan-2-yl]oxiran-2-yl]methoxy]silane
• CAS: 199284-29-2
• 化学式: C₂₂H₄₈O₃Si₂
• 分子量: 416.792
• InChiKey: OEORVMYQISOKGQ-DXBBTUNJSA-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：

  (2R,3R)-2-Methyl-3-((1R,2R)-1-methyl-2-triethylsilanyloxy-pentyl)-2-triethylsilanyloxymethyl-oxirane 在 2,6-二叔丁基-4-甲基吡啶 、 三乙基硅基三氟甲磺酸酯 作用下， 以91%的产率得到
  参考文献：
  名称：

  Synthesis of Four Diastereomeric 3,5-Dialkoxy-2,4-dimethylalkanals by a Simple Extension of the Non-Aldol Aldol Process to Bis(propionates)

  摘要：

  [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.

  DOI：

  10.1021/ol990619+
• 作为产物：
  描述：

  (2S,3R)-3-(Triethylsilyloxy)-2-methylhexanal 在 4-二甲氨基吡啶 、 dipotassium hydrogenphosphate 、 18-冠醚-6 、 双(三甲基硅烷基)氨基钾 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 、 红铝 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 22.25h， 生成 (2R,3R)-2-Methyl-3-((1R,2R)-1-methyl-2-triethylsilanyloxy-pentyl)-2-triethylsilanyloxymethyl-oxirane
  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.
• Use of the non-aldol aldol process in the synthesis of the C1–C11 fragment of the tedanolides: use of lactol ethers in place of tetrahydrofurans
  作者：Michael E Jung、Christopher P Lee

  DOI：10.1016/s0040-4039(00)01726-3

  日期：2000.12

  The use of a lactol methyl ether 23 in place of the simple tetrahydrofuran 11 allows for the high yielding non-aldol aldol process to occur without concomitant tetrahydropyran formation (cf 13) to give the desired product 24 in good yield. (C) 2000 Elsevier Science Ltd. All rights reserved.
• 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
  作者：Michael E. Jung、Derin C. D'Amico

  DOI：10.1021/ja972507o

  日期：1997.12.17

  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.
• 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.