1-Methoxy-1-(trimethylsiloxy)-2-(4-chlorophenyl)cyclopropane

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-Methoxy-1-(trimethylsiloxy)-2-(4-chlorophenyl)cyclopropane
• 化学式: C₁₃H₁₉ClO₂Si
• 分子量: 270.831
• InChiKey: YXPMVKRNNKZGKT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.02
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-Methoxy-1-(trimethylsiloxy)-2-(4-chlorophenyl)cyclopropane 在 噻吩-2-甲酸亚铜(I) 、 nickel(II) chloride hexahydrate 、 (3aS,3a'S,8aR,8a'R)-2,2'-(1-苯基丙烷-2,2-二基)双(8,8a-二氢-3aH-茚并[1,2-d]恶唑) 、 N-氟代双苯磺酰胺 作用下， 以 甲醇 、 丙酮 为溶剂， 反应 8.0h， 生成 (S)-4-(4-氯苯基)吡咯烷-2-酮
  参考文献：
  名称：

  对映选择性铜催化环丙醇和环丙酮酮缩醛的自由基开环氰化

  摘要：

  通过铜催化的自由基中继过程，开发了一种新的环丙醇及其衍生物的对映选择性氰化方法。各种环丙醇和环丙酮缩醛均与催化条件兼容，从而为β-羰基腈提供了出色的对映选择性。这些产品可以很容易地转化为手性γ-氨基酸衍生物和药物，例如（R）-baclofen。初步的机理研究支持了环丙氧基自由基的开环过程，随后是铜催化的苄基自由基的对映选择性氰化，以对映选择性的方式形成C-CN键。

  DOI：

  10.1002/adsc.202000202

文献信息

• Electron Transfer Profile of Cyclopropanone Acetals in the Nonirradiated Reaction with Tetracyanoethylene, Chloranil, and Dicyanodichlorobenzoquinone
  作者：Akira Oku、Manabu Abe、Masaharu Iwamoto

  DOI：10.1021/jo00103a043

  日期：1994.12

  The donor profiles of cyclopropanone acetals 1 and 2 were examined in the reactions with electron accepters (TCNE, DDQ, chloranil, and 1-cyanonaphthalene). With TCNE under nonirradiating conditions, an exclusive 2 + 2 cycloaddition took place stereospecifically with monosubstituted acetals 1a-c but nonstereospecifically with disubstituted acetals 1d,e. With quinones, a ring-opening of the cyclopropane and its coupling with the quinone took place to give the C (cyclopropane)-O (quinone) adduct 9 (with chloranil) or 10 (with DDQ), the latter of which underwent the elimination of a phenol to produce unsaturated esters 5 and 6. In addition, the intervention of the C (cyclopropane)-C (quinone) adduct 14 (with chloranil) or 15 (with DDQ), both as the precursor of 5 and 6, was also postulated. With 1-cyanonaphthalene, under photolysis, the cis/trans isomerization of 1 and 2 occurred. The results provided evidences that cyclopropanone acetals, in general, are prone to function as donors. The mechanism of the reaction with quinones, in particular, was investigated in detail.
• Enantioselective Copper‐Catalyzed Radical Ring‐Opening Cyanation of Cyclopropanols and Cyclopropanone Acetals
  作者：Lianqian Wu、Lei Wang、Pinghong Chen、Yin‐Long Guo、Guosheng Liu

  DOI：10.1002/adsc.202000202

  日期：2020.5.26

  copper‐catalyzed radical relay processes has been developed. Various cyclopropanols and cyclopropanone acetals are compatible to the catalytic conditions, providing β‐carbonyl nitriles with excellent enantioselectivity. These products can be readily converted to chiral γ‐amino acids derivatives and drugs such as (R)‐baclofen. Preliminary mechanistic studies have supported a ring‐opening process for cyclopropanoxy

  通过铜催化的自由基中继过程，开发了一种新的环丙醇及其衍生物的对映选择性氰化方法。各种环丙醇和环丙酮缩醛均与催化条件兼容，从而为β-羰基腈提供了出色的对映选择性。这些产品可以很容易地转化为手性γ-氨基酸衍生物和药物，例如（R）-baclofen。初步的机理研究支持了环丙氧基自由基的开环过程，随后是铜催化的苄基自由基的对映选择性氰化，以对映选择性的方式形成C-CN键。