(+/-)-tert-butyl 2-(2-benzoyl-3-phenylcyclopropyl)acetate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-tert-butyl 2-(2-benzoyl-3-phenylcyclopropyl)acetate
• 英文别名: tert-butyl 2-[(1S,2R,3R)-2-benzoyl-3-phenylcyclopropyl]acetate
• 化学式: C₂₂H₂₄O₃
• 分子量: 336.431
• InChiKey: JLTYZPLWBVPQMV-DFQSSKMNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  二乙基膦酰基乙酸叔丁酯 、 3,6-diphenyl-3,6-dihydro-1,2-dioxine 在 甲基锂 作用下， 以 四氢呋喃 为溶剂， 反应 3.5h， 以75%的产率得到(+/-)-tert-butyl 2-(2-benzoyl-3-phenylcyclopropyl)acetate
  参考文献：
  名称：

  An Improved Synthesis of Cyclopropanes from Stabilized Phosphonates and 1,2-Dioxines

  摘要：

  Addition of stabilized Horner-Wadsworth-Emmons (HWE) phosphonates to substituted 1,2-dioxines leads to diastereomerically pure di- and trisubstituted cyclopropanes in high yields and represents a viable alternative to ylides in the cyclopropanation reaction involving 1,2-dioxines. While yields are comparable, reaction times with these stabilized phosphonates were accelerated and the diastereoselectivity for this cyclopropanation reaction was significantly greater than for the previously reported examples employing ylides.

  DOI：

  10.1021/jo0110496

文献信息

• Mechanistic Investigations on the Reaction between 1,2-Dioxines and Bulky Stabilized Phosphorus Ylides:  An Efficient Route to Closely Related Cyclopropane Stereoisomers
  作者：Thomas D. Avery、Gary Fallon、Ben W. Greatrex、Simon M. Pyke、Dennis K. Taylor、Edward R. T. Tiekink

  DOI：10.1021/jo001599o

  日期：2001.11.1

  Importantly, enolate quenching of the intermediate 1-2lambda(5)-oxaphospholanes 4 prior to collapse results in an equilibrium mixture of intermediates 10 and 11 which have been fully characterized, and their formation is primarily a result of the steric bulk of the stabilized ester ylide. These intermediates (10/11) then collapse further and result in formation of the observed closely related cyclopropyl

  庞大的稳定化的亚烷基（2a-d）与一系列1,2-二恶英（1a-d）反应，从而以优异的收率和非对映异构体过量提供了各种官能化的环丙烷7。这与使用非块状酯基化物导致完全不同的环丙基系列的情况形成鲜明对比。通过隔离，光谱，温度，氘和加合效应研究的结合，可以提出由第二种途径形成环丙烷的机理。重要的是，中间体1-2lambda（5）-草酰膦4发生塌陷前的烯醇淬灭导致中间体10和11的平衡混合物得到充分表征，它们的形成主要是由于稳定酯的空间体积ylide。然后，这些中间体（10/11）进一步塌陷，导致形成观察到的密切相关的环丙基立体异构体7和8。此外，向这些反应中添加LiBr可以控制两个可能的环丙烷化途径中的哪一个占主导。最后，提出了最佳方案，这些方案证明了这种新的环丙烷化方法在密切相关的环丙基立体异构体的制备中的潜力。
• Exploitation of ylide steric bulk to alter cyclopropanation outcome during the reaction of 1,2-dioxines and stabilised phosphorus ylides
  作者：Thomas D. Avery、Ben W. Greatrex、Dennis K. Taylor、Edward R. T. Tiekink

  DOI：10.1039/b001975p

  日期：——

  A new approach for the synthesis of diastereomerically pure cyclopropanes from 1,2-dioxines and sterically bulky stabilised phosphorus ylides is presented.

  介绍了一种从 1,2-二氧杂环和立体笨重的稳定化磷酰化物合成非对映异构体纯环丙烷的新方法。
• An Improved Synthesis of Cyclopropanes from Stabilized Phosphonates and 1,2-Dioxines
  作者：Marc C. Kimber、Dennis K. Taylor

  DOI：10.1021/jo0110496

  日期：2002.5.1

  Addition of stabilized Horner-Wadsworth-Emmons (HWE) phosphonates to substituted 1,2-dioxines leads to diastereomerically pure di- and trisubstituted cyclopropanes in high yields and represents a viable alternative to ylides in the cyclopropanation reaction involving 1,2-dioxines. While yields are comparable, reaction times with these stabilized phosphonates were accelerated and the diastereoselectivity for this cyclopropanation reaction was significantly greater than for the previously reported examples employing ylides.