2-(4-chlorophenyl)-2-methylcyclobutanone | 1242029-74-8

• 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: 2-(4-chlorophenyl)-2-methylcyclobutanone
• 英文别名: 2-(4-Chlorophenyl)-2-methylcyclobutan-1-one
• CAS: 1242029-74-8
• 化学式: C₁₁H₁₁ClO
• 分子量: 194.661
• InChiKey: ASILLAPQAZLBKQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(4-chlorophenyl)-2-methylcyclobutanone 、 三甲基硅烷化重氮甲烷 在 scandium tris(trifluoromethanesulfonate) 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 1.5h， 生成
  参考文献：
  名称：

  Catalytic and Regioselective Ring Expansion of Arylcyclobutanones with Trimethylsilyldiazomethane. Ligand-Dependent Entry to β-Ketosilane or Enolsilane Adducts

  摘要：

  Divergent reactivity is uncovered in the homologation of arylcyclobutanones with trimethylsilyldiazomethane. With Sc(OTf)(3) as catalyst, enolsilanes are obtained with a high preference for methylene migration. By contrast, Sc(hfac)(3) gives beta-ketosilanes with both regio- and diastereocontrol. Each adduct affords the cyclopentanone upon hydrolysis.

  DOI：

  10.1021/ol101136a
• 作为产物：
  描述：

  1-(4-chlorophenyl)-1-(1-(phenylthio)cyclopropyl)ethanol 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 5.0h， 以43%的产率得到2-(4-chlorophenyl)-2-methylcyclobutanone
  参考文献：
  名称：

  Catalytic and Regioselective Ring Expansion of Arylcyclobutanones with Trimethylsilyldiazomethane. Ligand-Dependent Entry to β-Ketosilane or Enolsilane Adducts

  摘要：

  Divergent reactivity is uncovered in the homologation of arylcyclobutanones with trimethylsilyldiazomethane. With Sc(OTf)(3) as catalyst, enolsilanes are obtained with a high preference for methylene migration. By contrast, Sc(hfac)(3) gives beta-ketosilanes with both regio- and diastereocontrol. Each adduct affords the cyclopentanone upon hydrolysis.

  DOI：

  10.1021/ol101136a

文献信息

• Dual-Hydrogen-Bond Donor and Brønsted Acid Cocatalysis Enables Highly Enantioselective Protio-Semipinacol Rearrangement Reactions
  作者：Melanie A. S. Blackburn、Corin C. Wagen、M. Raul Bodrogean、Pamela M. Tadross、Andrew J. Bendelsmith、Dennis A. Kutateladze、Eric N. Jacobsen

  DOI：10.1021/jacs.3c02960

  日期：2023.7.19

  A catalytic protio-semipinacol ring-expansion reaction has been developed for the highly enantioselective conversion of tertiary vinylic cyclopropyl alcohols into cyclobutanone products bearing α-quaternary stereogenic centers. The method relies on the cocatalytic effect of a chiral dual-hydrogen-bond donor (HBD) with hydrogen chloride. Experimental evidence is provided for a stepwise mechanism where

  开发了一种催化原硫代半频那醇扩环反应，用于将叔乙烯环丙醇高度对映选择性转化为带有α-季立构中心的环丁酮产品。该方法依赖于手性双氢键供体（HBD）与氯化氢的共催化作用。实验证据证明了一种逐步机制，其中烯烃的质子化产生短寿命的高能碳正离子，随后进行 C-C 键迁移以产生对映体富集的产物。该研究将强酸/手性HBD共催化应用于弱碱性烯烃底物，为进一步研究涉及高能阳离子中间体的对映选择性反应奠定了基础。
• Catalytic and Regioselective Ring Expansion of Arylcyclobutanones with Trimethylsilyldiazomethane. Ligand-Dependent Entry to β-Ketosilane or Enolsilane Adducts
  作者：Jennifer A. Dabrowski、David C. Moebius、Andrew J. Wommack、Anne F. Kornahrens、Jason S. Kingsbury

  DOI：10.1021/ol101136a

  日期：2010.8.20

  Divergent reactivity is uncovered in the homologation of arylcyclobutanones with trimethylsilyldiazomethane. With Sc(OTf)(3) as catalyst, enolsilanes are obtained with a high preference for methylene migration. By contrast, Sc(hfac)(3) gives beta-ketosilanes with both regio- and diastereocontrol. Each adduct affords the cyclopentanone upon hydrolysis.