(4S,5S)-8-(benzyloxy)-5-(tert-butyldimethylsilyloxy)-4-methyloctanal | 1262206-07-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (4S,5S)-8-(benzyloxy)-5-(tert-butyldimethylsilyloxy)-4-methyloctanal
• 英文别名: (4S,5S)-5-[tert-butyl(dimethyl)silyl]oxy-4-methyl-8-phenylmethoxyoctanal
• CAS: 1262206-07-4
• 化学式: C₂₂H₃₈O₃Si
• 分子量: 378.627
• InChiKey: HQVZZFPTGAVYIQ-FPOVZHCZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.99
• 重原子数：
  26
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.68
• 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：

  (4S,5S)-8-(benzyloxy)-5-(tert-butyldimethylsilyloxy)-4-methyloctanal 、 1-三苯基膦-2-丙酮 以 苯 为溶剂， 反应 3.5h， 以172 mg的产率得到(5S,6S,E)-9-(benzyloxy)-6-(tert-butyldimethylsilyloxy)-5-methylnon-3-en-2-one
  参考文献：
  名称：

  Sequential One-Pot Isomerization-Wittig Olefination-Hydrogenation

  摘要：

  伯烯丙醇在 Pd(OH)2 存在下异构化为醛，并通过按顺序添加稳定的 Wittig 叶立德在一锅中同系为 α,β-不饱和羰基衍生物。当通过添加更多催化剂来延长反应时，在维蒂希烯化之后进行氢化步骤。此外，连续异构化-Wittig烯化-氧杂-迈克尔加成反应提供了具有高非对映选择性的四氢吡喃。

  DOI：

  10.1055/s-0030-1260232
• 作为产物：
  描述：

  4-苯基甲氧基-丁醛 在 2,6-二甲基吡啶 、 20 % Pd(OH)2/C 、 氢气 、 四氯化钛 、 二异丁基氢化铝 、 三乙胺 作用下， 以 正己烷 、 二氯甲烷 、 苯 为溶剂， 反应 2.42h， 生成 (4S,5S)-8-(benzyloxy)-5-(tert-butyldimethylsilyloxy)-4-methyloctanal
  参考文献：
  名称：

  Palladium Hydroxide Catalyzed Isomerization of Primary Allylic Alcohols to Aldehydes: Application to the Formal Synthesis of (−)-Brevisamide

  摘要：

  The Pd-catalyzed isomerization of primary allylic alcohols into the corresponding saturated aldehydes has been achieved at room temperature for the first time in good to excellent yields under mild conditions. The functional group compatibility in this reaction is studied, and this new methodology has been successfully applied in the synthesis of a C5-C13 tetrahydropyran ring system of (-)-brevisamide in seven steps.

  DOI：

  10.1021/ol102658d

文献信息

• Palladium Hydroxide Catalyzed Isomerization of Primary Allylic Alcohols to Aldehydes: Application to the Formal Synthesis of (−)-Brevisamide
  作者：Gowravaram Sabitha、Sambit Nayak、M. Bhikshapathi、J. S. Yadav

  DOI：10.1021/ol102658d

  日期：2011.2.4

  The Pd-catalyzed isomerization of primary allylic alcohols into the corresponding saturated aldehydes has been achieved at room temperature for the first time in good to excellent yields under mild conditions. The functional group compatibility in this reaction is studied, and this new methodology has been successfully applied in the synthesis of a C5-C13 tetrahydropyran ring system of (-)-brevisamide in seven steps.
• Sequential One-Pot Isomerization-Wittig Olefination-Hydrogenation
  作者：Gowravaram Sabitha、Sambit Nayak、M. Bhikshapathi、Maruthi Chittapragada、J. Yadav

  DOI：10.1055/s-0030-1260232

  日期：2011.11

  Primary allylic alcohols are isomerized to aldehydes in the presence of Pd(OH)2 and homologated to α,β-unsaturated carbonyl derivatives in one-pot by addition of stabilized Wittig ylides in a sequential fashion. When the reaction was prolonged by addition of more catalyst, a hydrogenation step succeeds the Wittig olefination. In addition, sequential isomerization-Wittig olefination-oxa-Michael addition reaction provides tetrahydropyran with high dia­stereoselectivity.

  伯烯丙醇在 Pd(OH)2 存在下异构化为醛，并通过按顺序添加稳定的 Wittig 叶立德在一锅中同系为 α,β-不饱和羰基衍生物。当通过添加更多催化剂来延长反应时，在维蒂希烯化之后进行氢化步骤。此外，连续异构化-Wittig烯化-氧杂-迈克尔加成反应提供了具有高非对映选择性的四氢吡喃。