(2'E,4S,5'S)-4-tert-Butyl-3-[5'-dimethylphenylsilyl-7'-oxo-2'-heptenoyl]-oxazolidin-2-one | 251908-42-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (2'E,4S,5'S)-4-tert-Butyl-3-[5'-dimethylphenylsilyl-7'-oxo-2'-heptenoyl]-oxazolidin-2-one
• 英文别名: (E,3S)-7-[(4S)-4-tert-butyl-2-oxo-1,3-oxazolidin-3-yl]-3-[dimethyl(phenyl)silyl]-7-oxohept-5-enal
• CAS: 251908-42-6
• 化学式: C₂₂H₃₁NO₄Si
• 分子量: 401.578
• InChiKey: QRTZOXZTFKTWMX-RBAMYAFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  63.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2'E,4S,5'S)-4-tert-Butyl-3-[5'-dimethylphenylsilyl-7'-oxo-2'-heptenoyl]-oxazolidin-2-one 在 三氟甲磺酸 、 B-methoxy-bis(2-isocaranyl)borane 、 boron trifluoride diacetate 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 34.41h， 生成 Methyl (2E,5S,7S)-7-benzyloxy-5-hydroxy-2,9-decanedienoate
  参考文献：
  名称：

  General and Asymmetric Synthesis of Protected 1,3,5-Triols with Pendant Functional Groups

  摘要：

  A stereoselective synthesis of enantiomerically purl 1,3,5-triols of any configuration has been developed. These triols carry suitable functional groups at the termini of the chain which should allow for easy and efficient coupling of two building blocks. The silyloxy-Cope rearrangement of syn-aldols was used to prepare a common advanced intermediate for the synthesis of all four stereoisomeric triols. Three synthetic operations-an allylboration, an oxidative desilylation, and a conjugate addition reaction-were employed to assemble the target molecules. Their terminal double bond may either be cleaved to give the corresponding aldehydes or oxidized to the methyl ketones in a Wacker process to provide access to two subunits for a coupling reaction.

  DOI：

  10.1002/(sici)1521-3765(19991001)5:10<2850::aid-chem2850>3.0.co;2-7
• 作为产物：
  描述：

  (S,E)‐3‐(but‐2‐enoyl)‐4‐(tert‐butyl)oxazolidin‐2‐one 在 三氟甲磺酸二丁硼 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 10.5h， 生成 (2'E,4S,5'S)-4-tert-Butyl-3-[5'-dimethylphenylsilyl-7'-oxo-2'-heptenoyl]-oxazolidin-2-one
  参考文献：
  名称：

  General and Asymmetric Synthesis of Protected 1,3,5-Triols with Pendant Functional Groups

  摘要：

  A stereoselective synthesis of enantiomerically purl 1,3,5-triols of any configuration has been developed. These triols carry suitable functional groups at the termini of the chain which should allow for easy and efficient coupling of two building blocks. The silyloxy-Cope rearrangement of syn-aldols was used to prepare a common advanced intermediate for the synthesis of all four stereoisomeric triols. Three synthetic operations-an allylboration, an oxidative desilylation, and a conjugate addition reaction-were employed to assemble the target molecules. Their terminal double bond may either be cleaved to give the corresponding aldehydes or oxidized to the methyl ketones in a Wacker process to provide access to two subunits for a coupling reaction.

  DOI：

  10.1002/(sici)1521-3765(19991001)5:10<2850::aid-chem2850>3.0.co;2-7

文献信息

• Highly Stereoselective and Efficient Synthesis of Functionalized Cyclohexanes with Multiple Stereocenters
  作者：Christoph Schneider、Oliver Reese

  DOI：10.1002/1521-3765(20020603)8:11<2585::aid-chem2585>3.0.co;2-c

  日期：2002.6.3

  Chiral 7-oxo-2-enimides 2, which were readily obtained through a silyloxy-Cope rearrangement of syn-aldol products 1, have proved to be versatile substrates for a one-step, highly efficient and stereoselective synthesis of functionalized cyclohexanes. Organocopper and organoaluminum reagents have been employed as nucleophiles that underwent a conjugate addition to the enimide structure of the Cope

  通过顺式醛醇缩合产物1的甲硅烷氧基-Cope重排容易获得的手性7-氧代-2-烯酰亚胺2已被证明是用于一步一步，高效且立体选择性地合成官能化环己烷的通用底物。有机铜和有机铝试剂已被用作亲核试剂，对Cope产品的亚胺结构进行了共轭加成。原位形成的烯醇化物在分子内羟醛或曼尼希反应中分别攻击醛或亚胺离子，分别以中等至良好的产率直接产生环己醇3和4和环己胺5，并具有良好的立体控制。
• General and Asymmetric Synthesis of Protected 1,3,5-Triols with Pendant Functional Groups
  作者：Christoph Schneider、Markus Rehfeuter

  DOI：10.1002/(sici)1521-3765(19991001)5:10<2850::aid-chem2850>3.0.co;2-7

  日期：1999.10.1

  A stereoselective synthesis of enantiomerically purl 1,3,5-triols of any configuration has been developed. These triols carry suitable functional groups at the termini of the chain which should allow for easy and efficient coupling of two building blocks. The silyloxy-Cope rearrangement of syn-aldols was used to prepare a common advanced intermediate for the synthesis of all four stereoisomeric triols. Three synthetic operations-an allylboration, an oxidative desilylation, and a conjugate addition reaction-were employed to assemble the target molecules. Their terminal double bond may either be cleaved to give the corresponding aldehydes or oxidized to the methyl ketones in a Wacker process to provide access to two subunits for a coupling reaction.