1-(tert-Butyldimethylsiloxy)-1-methoxyspiro<2.5>octane

• 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: 1-(tert-Butyldimethylsiloxy)-1-methoxyspiro<2.5>octane
• 英文别名: Tert-butyl-(2-methoxyspiro[2.5]octan-2-yl)oxy-dimethylsilane
• 化学式: C₁₅H₃₀O₂Si
• 分子量: 270.488
• InChiKey: GVAYDBULDSYNLF-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：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  对氰基苯乙酮 、 1-(tert-Butyldimethylsiloxy)-1-methoxyspiro<2.5>octane 在 magnesium(II) perchlorate 、 水 作用下， 以 乙腈 为溶剂， 反应 3.0h， 以28%的产率得到2,3-Bis(p-cyanophenyl)-2,3-butanediol
  参考文献：
  名称：

  Oxidative Ring-Opening Reaction of Cyclopropanone Acetals with Carbonyl Compounds via Photoinduced Electron Transfer. Generation of a .beta.-Carbonyl Radical Species and Its Application to the Synthesis of .gamma.-Hydroxy Ester Derivatives

  摘要：

  Photoinduced electron transfer (PET) reactions of 2-substituted or 2,2-disubstituted cyclopropanone methyl trialkylsilyl acetals 1a-e,g and 1-siloxy-2-oxabicyclo[3.1.0]hexane (1f) with carbonyl compounds 2 (benzophenone (2a), acetophenone (2b), 2-acetonaphthone (2c), 2-acetylpyridine (2d), 4-acetylbenzonitrile (2e), 2,3-butanedione (2f), and benzoyl cyanide (2g)) were examined in the presence of Mg(ClO4)(2). Carbon-carbon bond coupling products (gamma-hydroxy esters 3 or their derivative butyrolactones 4) between 1 and 2 were formed in good yields. A mechanism is proposed for the product formation which is initiated by the single electron transfer (SET) from 1 to the excited state of 2. The SET generates a transient pair of ion radicals, i.e. a ring-opened sec- or tert-beta-carbonyl radical from 1 and a ketyl radical ion from 2 stabilized by the Mg salt. This realizes a novel type of carbon-carbon bond formation at the sterically crowded beta-position of propanoates.

  DOI：

  10.1021/jo00115a022

文献信息

• Photoinduced electron transfer reaction of cyclopropanone acetals with arylmethyl methanesulfonate: generation of β-keto radical species and application to C–C bond formation
  作者：Manabu Abe、Akira Oku

  DOI：10.1039/c39940001673

  日期：——

  The photoinduced electron transfer reaction of the cyclopropanone acetals 1 with arylmethyl methanesulfonates 4 or 10 as electron acceptors was found to generate a transient pair of radicals, the β-keto radical 3 and the arylmethyl radical, which underwent a novel carbon–carbon bond formation reaction at the sterically hindered β-position of the esters.

  研究发现，环丙酮缩醛 1 与作为电子受体的芳基甲基甲烷磺酸盐 4 或 10 发生光诱导电子转移反应时，会产生一对瞬时自由基--δ-酮自由基 3 和芳基甲基自由基，这对自由基在酯的立体受阻δ位上发生了新的碳碳键形成反应。
• Oxidative Ring-Opening Reaction of Cyclopropanone Acetals with Carbonyl Compounds via Photoinduced Electron Transfer. Generation of a .beta.-Carbonyl Radical Species and Its Application to the Synthesis of .gamma.-Hydroxy Ester Derivatives
  作者：Manabu Abe、Akira Oku

  DOI：10.1021/jo00115a022

  日期：1995.5

  Photoinduced electron transfer (PET) reactions of 2-substituted or 2,2-disubstituted cyclopropanone methyl trialkylsilyl acetals 1a-e,g and 1-siloxy-2-oxabicyclo[3.1.0]hexane (1f) with carbonyl compounds 2 (benzophenone (2a), acetophenone (2b), 2-acetonaphthone (2c), 2-acetylpyridine (2d), 4-acetylbenzonitrile (2e), 2,3-butanedione (2f), and benzoyl cyanide (2g)) were examined in the presence of Mg(ClO4)(2). Carbon-carbon bond coupling products (gamma-hydroxy esters 3 or their derivative butyrolactones 4) between 1 and 2 were formed in good yields. A mechanism is proposed for the product formation which is initiated by the single electron transfer (SET) from 1 to the excited state of 2. The SET generates a transient pair of ion radicals, i.e. a ring-opened sec- or tert-beta-carbonyl radical from 1 and a ketyl radical ion from 2 stabilized by the Mg salt. This realizes a novel type of carbon-carbon bond formation at the sterically crowded beta-position of propanoates.