(S)-(+)-6-tert-butyldimethylsilyloxy-2H-pyran-3(6H)-one | 329684-96-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (S)-(+)-6-tert-butyldimethylsilyloxy-2H-pyran-3(6H)-one
• 英文别名: (2S)-2-[tert-butyl(dimethyl)silyl]oxy-2H-pyran-5-one
• CAS: 329684-96-0
• 化学式: C₁₁H₂₀O₃Si
• 分子量: 228.363
• InChiKey: KEVABZQAQGBKCA-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.49
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  甲基锂 、 (S)-(+)-6-tert-butyldimethylsilyloxy-2H-pyran-3(6H)-one 在 三甲基氯硅烷 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 0.67h， 以90%的产率得到(5R,6S)-6-{[tert-butyl(dimethyl)silyl]oxy}-5-methyldihydro-2H-pyran-3(4H)-one
  参考文献：
  名称：

  A Total Synthesis of (17S)-Hexahydro-TMC-69

  摘要：

  The cdc25A protein phosphatase inhibitor (7R,8R,10R, 17S)-hexahydro-TMC-69 (1a) has been synthesized in a stereoselective manner, starting from an enantiomerically pure pyranone (3) using Knoevenagel condensation as a key step.

  DOI：

  10.3987/com-06-10962
• 作为产物：
  描述：

  2,6-二氢-6-羟基-3(3H)-吡喃酮 在 2,6-二甲基吡啶 、 甲醇 、 manganese(IV) oxide 、 sodium tetrahydroborate 、 cerium(III) chloride 、 lipase AK 、 4 A molecular sieve 作用下， 以 phosphate buffer 、 二氯甲烷 、 丙酮 为溶剂， 反应 118.0h， 生成 (S)-(+)-6-tert-butyldimethylsilyloxy-2H-pyran-3(6H)-one
  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

• A Total Synthesis of (17S)-Hexahydro-TMC-69
  作者：Kazutoshi Sugawara、Yasuhiro Imanishi、Tomiki Hashiyama

  DOI：10.3987/com-06-10962

  日期：——

  The cdc25A protein phosphatase inhibitor (7R,8R,10R, 17S)-hexahydro-TMC-69 (1a) has been synthesized in a stereoselective manner, starting from an enantiomerically pure pyranone (3) using Knoevenagel condensation as a key step.
• Efficient and practical synthesis of both enantiomers of 6-silyloxy-3-pyranone derivatives
  作者：Kazutoshi Sugawara、Yasuhiro Imanishi、Tomiki Hashiyama

  DOI：10.1016/s0957-4166(00)00424-9

  日期：2000.11

  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.