2-[Tri(propan-2-yl)silyloxymethyl]pent-1-en-3-ol | 153996-38-4

• 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-[Tri(propan-2-yl)silyloxymethyl]pent-1-en-3-ol
• CAS: 153996-38-4
• 化学式: C₁₅H₃₂O₂Si
• 分子量: 272.503
• InChiKey: FMPXLWCANTWANE-UHFFFAOYSA-N

物化性质

• 沸点：
  317.5±30.0 °C(predicted)
• 密度：
  0.872±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.51
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  苯甲酸 、 2-[Tri(propan-2-yl)silyloxymethyl]pent-1-en-3-ol 在 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 为溶剂， 生成 3-(Benzoyloxy)-2-methylene-1-pentanol triisopropylsilyl ether
  参考文献：
  名称：

  Synthesis of Monoprotected 2-Alkylidene-1,3-propanediols by an Unusual SN2' Mitsunobu Reaction

  摘要：

  A simple and efficient route to monoprotected (E)- and (Z)-2-alkylidene-1,3-propanediols is described. The key step involves an unusual regio- and stereoselective S(N)2' Mitsunobu reaction of substituted 3-hydroxy-2-methylenealkanoates which are readily available from a Baylis-Hillman reaction between methyl acrylate and an aldehyde. These allylic alcohols, when treated with PPh(3), a carboxylic acid, and DEAD in THF at temperatures ranging from -40 degrees C to 22 degrees C, produced the corresponding 2-alkylidene-3-hydroxypropanoate derivatives (or (E)-2-(hydroxymethyl)-3-substituted-2-alkenoate derivatives) in >70% with S(N)2':S(N)2 ratio of 22:1 to >50:1. It was found that weak and bulky carboxylic acids and low temperatures favor S(N)2' addition. The reaction conditions were effective for alkyl substituted derivatives, but the addition of Et(3)N to the Mitsunobu conditions was necessary to improve the S(N)2':S(N)2 ratios for the vinyl 19 and phenyl 20 derivatives. The monoprotected (Z)- and (E)-2-alkylidene-1,3-propanediols can be efficiently synthesized by a three-step sequence involving either a transesterification, protection, and DIBAL-H reduction (>80% overall yield) or by the chemoselective reduction, protection, and ester cleavage (67% overall yield).

  DOI：

  10.1021/jo00126a046
• 作为产物：
  描述：

  3-hydroxy-2-methylene-pentanoic acid methyl ester 在 2,6-二甲基吡啶 、 二异丁基氢化铝 作用下， 以 二氯甲烷 为溶剂， 生成 2-[Tri(propan-2-yl)silyloxymethyl]pent-1-en-3-ol
  参考文献：
  名称：

  Synthesis of Monoprotected 2-Alkylidene-1,3-propanediols by an Unusual SN2' Mitsunobu Reaction

  摘要：

  A simple and efficient route to monoprotected (E)- and (Z)-2-alkylidene-1,3-propanediols is described. The key step involves an unusual regio- and stereoselective S(N)2' Mitsunobu reaction of substituted 3-hydroxy-2-methylenealkanoates which are readily available from a Baylis-Hillman reaction between methyl acrylate and an aldehyde. These allylic alcohols, when treated with PPh(3), a carboxylic acid, and DEAD in THF at temperatures ranging from -40 degrees C to 22 degrees C, produced the corresponding 2-alkylidene-3-hydroxypropanoate derivatives (or (E)-2-(hydroxymethyl)-3-substituted-2-alkenoate derivatives) in >70% with S(N)2':S(N)2 ratio of 22:1 to >50:1. It was found that weak and bulky carboxylic acids and low temperatures favor S(N)2' addition. The reaction conditions were effective for alkyl substituted derivatives, but the addition of Et(3)N to the Mitsunobu conditions was necessary to improve the S(N)2':S(N)2 ratios for the vinyl 19 and phenyl 20 derivatives. The monoprotected (Z)- and (E)-2-alkylidene-1,3-propanediols can be efficiently synthesized by a three-step sequence involving either a transesterification, protection, and DIBAL-H reduction (>80% overall yield) or by the chemoselective reduction, protection, and ester cleavage (67% overall yield).

  DOI：

  10.1021/jo00126a046

文献信息

• Synthesis of Monoprotected 2-Alkylidene-1,3-propanediols by an Unusual SN2' Mitsunobu Reaction
  作者：Andre B. Charette、Bernard Cote、Sylvie Monroc、Sylvie Prescott

  DOI：10.1021/jo00126a046

  日期：1995.10

  A simple and efficient route to monoprotected (E)- and (Z)-2-alkylidene-1,3-propanediols is described. The key step involves an unusual regio- and stereoselective S(N)2' Mitsunobu reaction of substituted 3-hydroxy-2-methylenealkanoates which are readily available from a Baylis-Hillman reaction between methyl acrylate and an aldehyde. These allylic alcohols, when treated with PPh(3), a carboxylic acid, and DEAD in THF at temperatures ranging from -40 degrees C to 22 degrees C, produced the corresponding 2-alkylidene-3-hydroxypropanoate derivatives (or (E)-2-(hydroxymethyl)-3-substituted-2-alkenoate derivatives) in >70% with S(N)2':S(N)2 ratio of 22:1 to >50:1. It was found that weak and bulky carboxylic acids and low temperatures favor S(N)2' addition. The reaction conditions were effective for alkyl substituted derivatives, but the addition of Et(3)N to the Mitsunobu conditions was necessary to improve the S(N)2':S(N)2 ratios for the vinyl 19 and phenyl 20 derivatives. The monoprotected (Z)- and (E)-2-alkylidene-1,3-propanediols can be efficiently synthesized by a three-step sequence involving either a transesterification, protection, and DIBAL-H reduction (>80% overall yield) or by the chemoselective reduction, protection, and ester cleavage (67% overall yield).