(+/-)-2-(2,2-diphenyl-vinyl)-oxirane | 399513-55-4

• 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-(2,2-diphenyl-vinyl)-oxirane
• 英文别名: (+/-)-2-(2,2-diphenylvinyl)oxirane；2-(2,2-diphenylvinyl)oxirane；2-(2,2-Diphenylethenyl)oxirane
• CAS: 399513-55-4
• 化学式: C₁₆H₁₄O
• 分子量: 222.287
• InChiKey: AYRHHXKOTJTXCJ-UHFFFAOYSA-N

物化性质

• 沸点：
  366.4±11.0 °C(Predicted)
• 密度：
  1.177±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-2-(2,2-diphenyl-vinyl)-oxirane 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 三氟化硼乙醚 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.83h， 生成 (+/-)-methyl (2E)-5-hydroxy-8,8-diphenylocta-2,7-dienoate
  参考文献：
  名称：

  Chemoselective Cross Metathesis of Bishomoallylic Alcohols:  Rapid Access to Fragment A of the Cryptophycins

  摘要：

  The racemic or enantioselective allylation of in situ formed beta,gamma-unsaturated aldehydes provides efficient access to bishomoallylic alcohols from readily available 2-vinyloxiranes. These products, when subjected to modified Grubbs cross metathesis conditions, afforded terminally homologated products in moderate to good yields with high E selectivity and without degradation of the enantiomeric excess. The compounds obtained through this two-step sequence yield fragments of an important and pharmacologically active family of cryptophycins.

  DOI：

  10.1021/ol049883f
• 作为产物：
  描述：

  β-苯基肉桂醛 在 正丁基锂 、 sodium hydride 、 sodium iodide 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 (+/-)-2-(2,2-diphenyl-vinyl)-oxirane
  参考文献：
  名称：

  通过路易斯酸产生的β，γ-不饱和醛的对映选择性烯丙基化诱导了2-乙烯基环氧乙烷的重排。

  摘要：

  [反应：见正文]已发现2-乙烯基氧杂环戊烷是β，γ-不饱和醛的优良替代物。这些有价值的亲电试剂是通过催化量的Sc（OTf）（3）处理2-乙烯基环氧乙烷而原位生成的，它们被基于α-pine烯的手性烯丙基化剂有效地捕获，从而以高收率和优异的选择性提供了双烯丙基烯丙醇。 。

  DOI：

  10.1021/ol016946a

文献信息

• Enantioselective Allylation of <i>β</i><i>,</i><i>γ</i>-Unsaturated Aldehydes Generated via Lewis Acid Induced Rearrangement of 2-Vinyloxiranes
  作者：Mark Lautens、Matthew L. Maddess、Effiette L. O. Sauer、Stéphane G. Ouellet

  DOI：10.1021/ol016946a

  日期：2002.1.1

  [reaction: see text] 2-Vinyloxiranes have been found to be excellent surrogates to beta,gamma-unsaturated aldehydes. These valuable electrophiles, generated in situ by treatment of a 2-vinyloxirane with a catalytic amount of Sc(OTf)(3), are effectively trapped by the chiral allylating agents based on alpha-pinene, affording bishomoallylic alcohols in high yield and excellent selectivity.

  [反应：见正文]已发现2-乙烯基氧杂环戊烷是β，γ-不饱和醛的优良替代物。这些有价值的亲电试剂是通过催化量的Sc（OTf）（3）处理2-乙烯基环氧乙烷而原位生成的，它们被基于α-pine烯的手性烯丙基化剂有效地捕获，从而以高收率和优异的选择性提供了双烯丙基烯丙醇。 。
• Contemporaneous Dual Catalysis: Aldol Products from Non‐Carbonyl Substrates
  作者：Barry M. Trost、Jacob S. Tracy

  DOI：10.1002/chem.201502973

  日期：2015.10.19

  carbon–carbon bond‐forming reactions vital to modern organic synthesis. Despite the attention this reaction has received, issues related to chemo‐ and regioselectivity as well as reactivity of readily enolizable electrophiles remain. To help overcome these limitations, a new direct approach toward aldol products that does not rely upon carbonyl substrates is described. This approach employs room‐temperature

  醛醇缩合反应是一类重要的原子-经济碳-碳键形成反应，对现代有机合成至关重要。尽管该反应受到关注，但仍存在与化学和区域选择性以及易于烯化的亲电试剂的反应性有关的问题。为了帮助克服这些局限性，描述了一种不依赖羰基底物的直接生产羟醛产物的新方法。该方法采用室温下同时进行的镧/钒双重催化，其中钒催化的1,3-烯丙醇转位与镧催化的Meinwald环氧化物原位结合可直接形成醛醇产物。
• Preparation of Homoallylic Homopropargylic Alcohols from 2-Vinyloxiranes
  作者：Matthew L. Maddess、Mark Lautens

  DOI：10.1021/ol051326l

  日期：2005.8.1

  beta, gamma-Unsaturated aldehydes generated in situ by treatment of 2-vinyloxiranes with a catalytic amount of Sc(OTf)3 or (BFOEt2)-O-. are effectively trapped by B-allenyl-9-BBN to afford homoallylic homopropargylic alcohols in high yield. An enantioselective version has been demonstrated, and a convenient synthesis of 9-allenyl-9-BBN is described.
• Chemoselective Cross Metathesis of Bishomoallylic Alcohols:  Rapid Access to Fragment A of the Cryptophycins
  作者：Mark Lautens、Matthew L. Maddess

  DOI：10.1021/ol049883f

  日期：2004.6.1

  The racemic or enantioselective allylation of in situ formed beta,gamma-unsaturated aldehydes provides efficient access to bishomoallylic alcohols from readily available 2-vinyloxiranes. These products, when subjected to modified Grubbs cross metathesis conditions, afforded terminally homologated products in moderate to good yields with high E selectivity and without degradation of the enantiomeric excess. The compounds obtained through this two-step sequence yield fragments of an important and pharmacologically active family of cryptophycins.