[(3aS,7aS)-6-(methoxymethoxymethyl)spiro[3a,7a-dihydro-1,3-benzodioxole-2,1'-cyclohexane]-4-yl]oxy-trimethylsilane | 221097-96-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [(3aS,7aS)-6-(methoxymethoxymethyl)spiro[3a,7a-dihydro-1,3-benzodioxole-2,1'-cyclohexane]-4-yl]oxy-trimethylsilane
• CAS: 221097-96-7
• 化学式: C₁₈H₃₀O₅Si
• 分子量: 354.519
• InChiKey: WKSPSXVHSVVAAL-RDJZCZTQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.73
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [(3aS,7aS)-6-(methoxymethoxymethyl)spiro[3a,7a-dihydro-1,3-benzodioxole-2,1'-cyclohexane]-4-yl]oxy-trimethylsilane 在 二甲基二环氧乙烷 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以70%的产率得到(3aS,7R,7aS)-7-hydroxy-6-(methoxymethoxymethyl)spiro[7,7a-dihydro-3aH-1,3-benzodioxole-2,1'-cyclohexane]-4-one
  参考文献：
  名称：

  Studies toward the construction of the allyltrisulfide component in esperamicin-A1 from 5-ketoshikimic acid derivatives: Part 2

  摘要：

  The MOM protected keto alcohol 7 was successfully converted to the silyl enol ether 4 by reaction with BSA. Reaction of this intermediate with dioxirane led to formation of allylic alcohol 10. Lactone 15 was obtained by reaction of tosylate 14 with the cuprate reagent derived from ethyl bromoacetate. Through a short sequence of reactions this 5-membered lactone was isomerized to the target lactone product 18. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)02400-9
• 作为产物：
  描述：

  (Z)-trimethylsilyl N-trimethylsilylacetimidate 、 (3aS,7aS)-6-(methoxymethoxymethyl)spiro[5,7a-dihydro-3aH-1,3-benzodioxole-2,1'-cyclohexane]-4-one 以 乙腈 为溶剂， 反应 1.0h， 生成 [(3aS,7aS)-6-(methoxymethoxymethyl)spiro[3a,7a-dihydro-1,3-benzodioxole-2,1'-cyclohexane]-4-yl]oxy-trimethylsilane
  参考文献：
  名称：

  Studies toward the construction of the allyltrisulfide component in esperamicin-A1 from 5-ketoshikimic acid derivatives: Part 2

  摘要：

  The MOM protected keto alcohol 7 was successfully converted to the silyl enol ether 4 by reaction with BSA. Reaction of this intermediate with dioxirane led to formation of allylic alcohol 10. Lactone 15 was obtained by reaction of tosylate 14 with the cuprate reagent derived from ethyl bromoacetate. Through a short sequence of reactions this 5-membered lactone was isomerized to the target lactone product 18. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)02400-9

文献信息

• Stereochemistry of Vinylogous Rubottom Oxidation of Proline-Fused Cyclohexadienol Silyl Ether
  作者：Hidetoshi Tokuyama、Kentaro Okano、Shun Okaya、Taichi Kurogi、Hideto Fujiwara

  DOI：10.3987/com-14-s(k)62

  日期：——

  The steric effect of vinylogous Rubottom oxidation of proline-fused cyclohexadienol silyl ether was investigated. The facial selectivity in the oxidation is governed by a synergistic effect of the proximal ester and a protective group on the nitrogen.