(+/-)-cis-1-<(Triisopropylsilyl)oxy>-4-hexen-2-ol | 152563-62-7

• 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: (+/-)-cis-1-<(Triisopropylsilyl)oxy>-4-hexen-2-ol
• 英文别名: (+/-)-cis-1-[(Triisopropylsilyl)oxy]-4-hexen-2-ol；(Z)-1-tri(propan-2-yl)silyloxyhex-4-en-2-ol
• CAS: 152563-62-7
• 化学式: C₁₅H₃₂O₂Si
• 分子量: 272.503
• InChiKey: ZFLHRNCSLYGRIL-HJWRWDBZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.51
• 重原子数：
  18.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  二氧化碳 、 (+/-)-cis-1-<(Triisopropylsilyl)oxy>-4-hexen-2-ol 在 正丁基锂 、 碘 作用下， 生成 (+/-)-(3R*,5S*,1'S*)-5-(1-Iodoethyl)-3-<((triisopropylsilyl)oxy)methyl>-2,6-dioxacyclohexanone 、 (+/-)-(3R*,5R*,1'R*)-5-(1-Iodoethyl)-3-<((triisopropylsilyl)oxy)methyl>-2,6-dioxacyclohexanone
  参考文献：
  名称：

  Stereochemistry of the iodocarbonatation of cis- and trans-3-methyl-4-pentene-1,2-diols: the unusual formation of several anti iodo carbonates

  摘要：

  A study on the stereoselective preparation of a series of 3-methyl-4,5-epoxy alcohols as an entry to polypropionates was undertaken. Initially, the opening of cis and trans TIPS-protected 2,3-epoxy butanols by propynyldiethylalane showed an excellent regioselectivity favoring the monoprotected 1,2-diol products. The resulting propargylic alcohols were stereoselectively reduced to the cis and trans 1-[(triisopropylsilyl)oxy]-3-methyl-4-hexen-2-ols. Iodocarbonatation of these four isomeric homoallylic alcohols was carried out and the stereochemistry of the intermediate iodo carbonates established. Interestingly, a complete anti selectivity (>20:1 anti:syn) was observed when both the syn 3-methyl and cis double-bond geometry were present (3b, 10, and 20). The anti relative configuration for all of the iodo carbonates was established by NMR, and that of 5b was confirmed by X-ray crystallography. This study demonstrated that the relative stereochemistry of the hydroxyl and C(3) methyl groups in combination with the cis or trans geometry of the alkene exerts a significant effect on the stereochemical outcome of the iodocarbonatation reaction. Methanolysis of the iodo carbonates produced the desired 3-methyl-4,5-epoxy alcohols. The application of this chemistry to the reiterative synthesis of polypropionates was carried out with epoxy alcohol 4a (anti isomer), producing a new homologated epoxy alcohol, 22, with six contiguous stereocenters in a highly stereoselective manner.

  DOI：

  10.1021/jo00073a027
• 作为产物：
  描述：

  三异丙基氯硅烷 在 palladium on activated charcoal 喹啉 、 4-二甲氨基吡啶 、 正丁基锂 、 TEA 、 氢气 、 氯化二乙基铝 作用下， 以 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 52.0h， 生成 (+/-)-cis-1-<(Triisopropylsilyl)oxy>-4-hexen-2-ol
  参考文献：
  名称：

  Stereochemistry of the iodocarbonatation of cis- and trans-3-methyl-4-pentene-1,2-diols: the unusual formation of several anti iodo carbonates

  摘要：

  A study on the stereoselective preparation of a series of 3-methyl-4,5-epoxy alcohols as an entry to polypropionates was undertaken. Initially, the opening of cis and trans TIPS-protected 2,3-epoxy butanols by propynyldiethylalane showed an excellent regioselectivity favoring the monoprotected 1,2-diol products. The resulting propargylic alcohols were stereoselectively reduced to the cis and trans 1-[(triisopropylsilyl)oxy]-3-methyl-4-hexen-2-ols. Iodocarbonatation of these four isomeric homoallylic alcohols was carried out and the stereochemistry of the intermediate iodo carbonates established. Interestingly, a complete anti selectivity (>20:1 anti:syn) was observed when both the syn 3-methyl and cis double-bond geometry were present (3b, 10, and 20). The anti relative configuration for all of the iodo carbonates was established by NMR, and that of 5b was confirmed by X-ray crystallography. This study demonstrated that the relative stereochemistry of the hydroxyl and C(3) methyl groups in combination with the cis or trans geometry of the alkene exerts a significant effect on the stereochemical outcome of the iodocarbonatation reaction. Methanolysis of the iodo carbonates produced the desired 3-methyl-4,5-epoxy alcohols. The application of this chemistry to the reiterative synthesis of polypropionates was carried out with epoxy alcohol 4a (anti isomer), producing a new homologated epoxy alcohol, 22, with six contiguous stereocenters in a highly stereoselective manner.

  DOI：

  10.1021/jo00073a027