(1S,2S)-1-Methyl-2-(hydroxymethyl)-2-<(R)-3-methyl-4-<(tetrahydropyranyl)oxy>butyl>oxirane | 143819-20-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (1S,2S)-1-Methyl-2-(hydroxymethyl)-2-<(R)-3-methyl-4-<(tetrahydropyranyl)oxy>butyl>oxirane
• 英文别名: [(2S,3S)-3-methyl-2-[(3R)-3-methyl-4-(oxan-2-yloxy)butyl]oxiran-2-yl]methanol
• CAS: 143819-20-9；143900-01-0；143900-06-5；143900-07-6
• 化学式: C₁₄H₂₆O₄
• 分子量: 258.358
• InChiKey: PEUUPECKKOLCEZ-UDRMKVCMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  51.2
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,2S)-1-Methyl-2-(hydroxymethyl)-2-<(R)-3-methyl-4-<(tetrahydropyranyl)oxy>butyl>oxirane 在 甲醇 、 lithium aluminium tetrahydride 、 草酰氯 、 二甲基氯化铝 、 4-甲基苯磺酸吡啶 、 二甲基亚砜 、 三乙胺 、 三甲氧基磷 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 151.5h， 生成 (1S,2R,E)-2-Methyl-5-ethylidenecyclohexanol
  参考文献：
  名称：

  On the mechanism of Lewis acid promoted ene cyclizations of .omega.-unsaturated aldehydes

  摘要：

  The diastereomerically labeled d1 enals 1 and 2 were prepared from (S)-3-bromo-2-methylpropanol 5 by a sequence involving homologation to the allylic alcohol 13 and Sharpless epoxidation to either the alpha- or the beta-epoxide diastereomers 14 or 15. Reduction with LiAlD4 afforded the diastereomerically deuterated diols 16 and 20, respectively. Deoxygenation of the thionocarbonate derivatives 17 and 21 followed by THP ether cleavage and Swern oxidation afforded aldehydes 1 and 2. The undeuterated aldehyde 28 was similarly prepared. Cyclization of 1 and 2 with Me2AlCl afforded the cis-(E)-ethylidenecyclohexanols 3 and 4, respectively, as the major products in accord with a mechanism involving internal proton or deuteron transfer from the vinylic CHD grouping to the aldehyde carbonyl. Product ratios (E:Z, cis:trans) from the two aldehydes were significantly different, indicative of a substantial isotope effect.

  DOI：

  10.1021/jo00048a016
• 作为产物：
  描述：

  (3R)-3-甲基-4-[(四氢-2H-吡喃-2-基)氧基]-丁腈 在 咪唑 、 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 sodium tetrahydroborate 、 L-(+)-酒石酸二异丙酯 、 4 A molecular sieve 、 碘 、 sodium hydride 、 二异丁基氢化铝 、 三苯基膦 作用下， 以 甲醇 、 异辛烷 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 17.17h， 生成 (1S,2S)-1-Methyl-2-(hydroxymethyl)-2-<(R)-3-methyl-4-<(tetrahydropyranyl)oxy>butyl>oxirane
  参考文献：
  名称：

  On the mechanism of Lewis acid promoted ene cyclizations of .omega.-unsaturated aldehydes

  摘要：

  The diastereomerically labeled d1 enals 1 and 2 were prepared from (S)-3-bromo-2-methylpropanol 5 by a sequence involving homologation to the allylic alcohol 13 and Sharpless epoxidation to either the alpha- or the beta-epoxide diastereomers 14 or 15. Reduction with LiAlD4 afforded the diastereomerically deuterated diols 16 and 20, respectively. Deoxygenation of the thionocarbonate derivatives 17 and 21 followed by THP ether cleavage and Swern oxidation afforded aldehydes 1 and 2. The undeuterated aldehyde 28 was similarly prepared. Cyclization of 1 and 2 with Me2AlCl afforded the cis-(E)-ethylidenecyclohexanols 3 and 4, respectively, as the major products in accord with a mechanism involving internal proton or deuteron transfer from the vinylic CHD grouping to the aldehyde carbonyl. Product ratios (E:Z, cis:trans) from the two aldehydes were significantly different, indicative of a substantial isotope effect.

  DOI：

  10.1021/jo00048a016

文献信息

• On the mechanism of Lewis acid promoted ene cyclizations of .omega.-unsaturated aldehydes
  作者：James A. Marshall、Marc W. Andersen

  DOI：10.1021/jo00048a016

  日期：1992.10

  The diastereomerically labeled d1 enals 1 and 2 were prepared from (S)-3-bromo-2-methylpropanol 5 by a sequence involving homologation to the allylic alcohol 13 and Sharpless epoxidation to either the alpha- or the beta-epoxide diastereomers 14 or 15. Reduction with LiAlD4 afforded the diastereomerically deuterated diols 16 and 20, respectively. Deoxygenation of the thionocarbonate derivatives 17 and 21 followed by THP ether cleavage and Swern oxidation afforded aldehydes 1 and 2. The undeuterated aldehyde 28 was similarly prepared. Cyclization of 1 and 2 with Me2AlCl afforded the cis-(E)-ethylidenecyclohexanols 3 and 4, respectively, as the major products in accord with a mechanism involving internal proton or deuteron transfer from the vinylic CHD grouping to the aldehyde carbonyl. Product ratios (E:Z, cis:trans) from the two aldehydes were significantly different, indicative of a substantial isotope effect.