(2'RS,3R)-3-methyl-4-(2-tetrahydropyranyloxy)butanal | 170572-77-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (2'RS,3R)-3-methyl-4-(2-tetrahydropyranyloxy)butanal
• 英文别名: Butanal, 3-methyl-4-[(tetrahydro-2H-pyran-2-yl)oxy]-, (3R)-；(3R)-3-methyl-4-(oxan-2-yloxy)butanal
• CAS: 170572-77-7
• 化学式: C₁₀H₁₈O₃
• 分子量: 186.251
• InChiKey: CSDPTDSQXVUMRM-YHMJZVADSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2'RS,3R)-3-methyl-4-(2-tetrahydropyranyloxy)butanal 在 咪唑 、 sodium tetrahydroborate 、 碘 、 sodium hydride 、 三苯基膦 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 14.67h， 生成 (R)-Methyl 2-(dimethylphosphono)-5-methyl-6-<(tetrahydropyranyl)oxy>hexanoate
  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：

  (R)-(+)-2-methyl-3-(tetrahydro-2-pyranyloxy)-propyl-p-toluenesulfonate 在 二异丁基氢化铝 作用下， 以 甲醇 、 六甲基磷酰三胺 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 12.5h， 生成 (2'RS,3R)-3-methyl-4-(2-tetrahydropyranyloxy)butanal
  参考文献：
  名称：

  氧固醇：27-羟基胆固醇及其放射性标记的类似物。

  摘要：

  我们描述了合成27-羟基胆固醇的便捷和立体选择途径。还通过该方法合成了其放射性标记的类似物，具有高比放射性（55 Ci / mmol）的22，23 di [（3）H] -27-羟基胆固醇。朱莉娅类固醇22砜与醛的缩合反应导致类固醇主链上添加了23-27碳侧链结构单元。在该反应中形成的β-羟基砜部分被钠汞齐还原生成22-23个不饱和键。用氢或tri提供的底物进一步还原以合成标题化合物。

  DOI：

  10.1016/s0039-128x(00)00099-4

文献信息

• General synthetic approach to bicyclo[9.3.0]tetradecenone: a versatile intermediate to clavulactone and clavirolides
  作者：Bingfeng Sun、Xingxiang Xu

  DOI：10.1016/j.tetlet.2005.09.106

  日期：2005.11

  An efficient and stereoselective approach to the bicyclo[9.3.0]tetradecenone core structure of clavulactone starting from readily and abundantly available 2-methyl-1,3-cyclopentandione employing microbial desymmetrization and cyanohydrin alkylation as the key steps is described. The synthetic route described herein is applicable to the syntheses of the core structures of Clavirolides A-F. (c) 2005 Elsevier Ltd. All rights reserved.
• Synthesis of (25R)-cholest-5-ene-3β, 26-diol and its radiolabeled analog
  作者：Thomas E. D'Ambra、Norman B. Javitt、Koji Nakanishi、Tadeusz Warchol

  DOI：10.1016/s0040-4039(97)00750-8

  日期：1997.6

  A new, convenient and stereoselective route to the synthesis of (25R)-cholest-5-ene-3 beta,26-diol (1) and its radiolabeled analog 4 is described. The key step is a Julia condensation of sulfone 6 with aldehyde 12 to furnish compound 13. Further reduction of the alpha-hydroxysulfone moiety afforded 22,23-unsaturated i-steroid 14. The double bond was reduced by hydrogen and by tritium to provide substrates for the preparation of 1 and 4, respectively. (C) 1997 Elsevier Science Ltd.
• Stereospecific rearrangement of α-hydroxyepoxide: efficient approach to the trans-bicyclo[9.3.0]tetradecane core en route to clavulactone
  作者：Bingfeng Sun、Xingxiang Xu

  DOI：10.1016/j.tetlet.2005.11.021

  日期：2006.1

  We document a synthetic route to trans-bicyclo[9.3.0]tetradecanes. The strategy is based oil a quantitative and stereospecific Lewis acid mediated rearrangement of alpha-hydroxyepoxide to beta-hydroxyketone, which paved the way for the synthesis of clavulactone and clavirolides. (c) 2005 Elsevier Ltd. All rights reserved.
• 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.
• Oxysterols: 27-hydroxycholesterol and its radiolabeled analog
  作者：T D'Ambra

  DOI：10.1016/s0039-128x(00)00099-4

  日期：2000.7

  describe a convenient and stereoselective route to the synthesis of 27-hydroxycholesterol. Also its radiolabeled analog, 22, 23 di [(3)H]-27-hydroxycholesterol with high specific radioactivity (55 Ci/mmol) was synthesized by this method. Julia condensation of steroidal 22-sulfone with aldehyde, led to the addition of the 23-27 carbon side chain building block to the steroid backbone. Formed in this

  我们描述了合成27-羟基胆固醇的便捷和立体选择途径。还通过该方法合成了其放射性标记的类似物，具有高比放射性（55 Ci / mmol）的22，23 di [（3）H] -27-羟基胆固醇。朱莉娅类固醇22砜与醛的缩合反应导致类固醇主链上添加了23-27碳侧链结构单元。在该反应中形成的β-羟基砜部分被钠汞齐还原生成22-23个不饱和键。用氢或tri提供的底物进一步还原以合成标题化合物。