4-Methyl-3-tri(propan-2-yl)silyloxypent-4-enal | 1000004-73-8

• 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: 4-Methyl-3-tri(propan-2-yl)silyloxypent-4-enal
• CAS: 1000004-73-8
• 化学式: C₁₅H₃₀O₂Si
• 分子量: 270.488
• InChiKey: SESIYUGUENAEST-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.71
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-Methyl-3-tri(propan-2-yl)silyloxypent-4-enal 、 tert-butyl-diphenyl-[2-pyridin-2-ylsulfanyl-2-tri(propan-2-yl)silyloxyethenoxy]silane 在 zinc(II) chloride 作用下， 以 二氯甲烷 为溶剂， 反应 240.0h， 生成 (3S,4S)-3-[tert-butyl(diphenyl)silyl]oxy-4-[(2R)-3-methyl-2-tri(propan-2-yl)silyloxybut-3-enyl]oxetan-2-one 、
  参考文献：
  名称：

  Diastereoselective Synthesis of Tetrahydrofurans via Mead Reductive Cyclization of Keto-β-Lactones Derived from the Tandem Mukaiyama Aldol Lactonization (TMAL) Process

  摘要：

  [Graphics]The development of a diastereoselective, three-step strategy for the construction of substituted tetrahydrofurans from alkenyl aldehydes based on the tandem Mukaiyama aldol-lactonization process and Mead reductive cyclization of keto beta-lactones is reported. Stereochemical outcomes of the TMAL process are consistent with models established for Lewis acid-mediated additions to a-benzyloxy and beta-silyloxy aldehydes while reductions of the five-membered oxocarbenium ions are consistent with Woerpel's models. Further rationalization for observed high diastereoselectivity in reductions of alpha-silyloxy 5-membered oxocarbenium ions based on stereoelectronic effects are posited. A diagnostic trend for coupling constants of gamma-benzyloxy beta-lactones was observed that should enable assignment of the relative configuration of these systems.

  DOI：

  10.1021/jo7014246
• 作为产物：
  描述：

  在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以81%的产率得到4-Methyl-3-tri(propan-2-yl)silyloxypent-4-enal
  参考文献：
  名称：

  Diastereoselective Synthesis of Tetrahydrofurans via Mead Reductive Cyclization of Keto-β-Lactones Derived from the Tandem Mukaiyama Aldol Lactonization (TMAL) Process

  摘要：

  [Graphics]The development of a diastereoselective, three-step strategy for the construction of substituted tetrahydrofurans from alkenyl aldehydes based on the tandem Mukaiyama aldol-lactonization process and Mead reductive cyclization of keto beta-lactones is reported. Stereochemical outcomes of the TMAL process are consistent with models established for Lewis acid-mediated additions to a-benzyloxy and beta-silyloxy aldehydes while reductions of the five-membered oxocarbenium ions are consistent with Woerpel's models. Further rationalization for observed high diastereoselectivity in reductions of alpha-silyloxy 5-membered oxocarbenium ions based on stereoelectronic effects are posited. A diagnostic trend for coupling constants of gamma-benzyloxy beta-lactones was observed that should enable assignment of the relative configuration of these systems.

  DOI：

  10.1021/jo7014246