(3R,6R)-cis-6-(tert-butyldimethylsilyloxy)-3,6-dihydro-2H-pyran-3-yl acetate | 329684-94-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (3R,6R)-cis-6-(tert-butyldimethylsilyloxy)-3,6-dihydro-2H-pyran-3-yl acetate
• 英文别名: [(3S,6R)-6-[tert-butyl(dimethyl)silyl]oxy-3,6-dihydro-2H-pyran-3-yl] acetate
• CAS: 329684-94-8
• 化学式: C₁₃H₂₄O₄Si
• 分子量: 272.417
• InChiKey: ANFBFGQUEHXORK-NWDGAFQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.85
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3R,6R)-cis-6-(tert-butyldimethylsilyloxy)-3,6-dihydro-2H-pyran-3-yl acetate 、 烯丙基三甲基硅烷 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 1.25h， 以91%的产率得到(3R,6S)-trans-6-allyl-3,6-dihydro-2H-pyran-3-yl acetate
  参考文献：
  名称：

  Efficient and practical synthesis of both enantiomers of 6-silyloxy-3-pyranone derivatives

  摘要：

  Lipase catalyzed kinetic resolution of racemic cis-6-(tert-butyldimethylsilyloxy)-3,6-dihydro-2H-pyran-3-ol (rac)-1 was achieved in high enantiomeric excess. Transesterification of (rac)-1 with vinylacetate in 'BuOMe yielded the alcohol (3S,6R)-1 in 99.0% ee, whereas (3R,6S)-1 was obtained, in 99.0% ee, by the lipase catalyzed ester hydrolysis of acetate (3R,6S)-2, which was obtained along with the transesterification. Both (3S,6R)-1 and (3R,6S)-1 were subjected to oxidation to provide the corresponding 6-silyloxy-3-pyranone (6R)-3 and (6S)-3, respectively. Application to the synthesis of 7, which is the key intermediate of asymmetric synthesis of pseudomonic acid A 9 is also described. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00424-9
• 作为产物：
  描述：

  (±)-cis-6-((tert-butyldimethylsilyl)oxy)-3,6-dihydro-2H-pyran-3-ol 在 lipase AK 、 4 A molecular sieve 作用下， 以 phosphate buffer 、 丙酮 为溶剂， 反应 108.0h， 生成 (3R,6R)-cis-6-(tert-butyldimethylsilyloxy)-3,6-dihydro-2H-pyran-3-yl acetate
  参考文献：
  名称：

  Efficient and practical synthesis of both enantiomers of 6-silyloxy-3-pyranone derivatives

  摘要：

  Lipase catalyzed kinetic resolution of racemic cis-6-(tert-butyldimethylsilyloxy)-3,6-dihydro-2H-pyran-3-ol (rac)-1 was achieved in high enantiomeric excess. Transesterification of (rac)-1 with vinylacetate in 'BuOMe yielded the alcohol (3S,6R)-1 in 99.0% ee, whereas (3R,6S)-1 was obtained, in 99.0% ee, by the lipase catalyzed ester hydrolysis of acetate (3R,6S)-2, which was obtained along with the transesterification. Both (3S,6R)-1 and (3R,6S)-1 were subjected to oxidation to provide the corresponding 6-silyloxy-3-pyranone (6R)-3 and (6S)-3, respectively. Application to the synthesis of 7, which is the key intermediate of asymmetric synthesis of pseudomonic acid A 9 is also described. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00424-9

文献信息

• ¹³C NMR Analysis of 3,6-Dihydro-2<i>H</i>-pyrans: Assignment of Remote Stereochemistry Using Axial Shielding Effects
  作者：Mark J. Bartlett、Peter T. Northcote、Matthias Lein、Joanne E. Harvey

  DOI：10.1021/jo500678k

  日期：2014.6.20

  The rational analysis of 13C NMR axial shielding effects has enabled the assignment of remote relative stereochemistry in 3,6-oxygen-substituted 3,6-dihydro-2H-pyrans. Comparison of the 13C NMR shifts of equivalent centers in cis- and trans-substituted 3,6-dihydro-2H-pyrans allows the relative configuration at the C3 and C6 positions to be defined in diastereoisomeric mixtures. Density functional calculations

  对13 C NMR轴向屏蔽效应的合理分析已使3,6-氧-取代的3,6-二氢-2 H-吡喃具有较远的相对立体化学。比较顺式和反式取代的3,6-二氢-2 H-吡喃中等价中心的13 C NMR位移，可以在非对映异构体混合物中定义C3和C6位置的相对构型。密度泛函计算用于验证该方法并评估环系统中存在的构象偏差。最终，计算化学与这13种方法的耦合基于13 C NMR的方法为单一非对映异构体的立体化学分配提供了可靠且方便的方法。该方法为先前用于确定3，6-二氢-2 H-吡喃的相对构型的方法提供了一种简便且互补的替代方法。