2,2,2-trifluoroethyl 2,3-butadienoate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2,2,2-trifluoroethyl 2,3-butadienoate
• 英文别名: 2,2,2-trifluoroethylbuta-2,3-dienoate
• 化学式: C₆H₅F₃O₂
• 分子量: 166.1
• InChiKey: PFNPLEOLHKHBKO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  环戊二烯 、 2,2,2-trifluoroethyl 2,3-butadienoate 在 (3aS)-1-(2-methylphenyl)-3,3-diphenyl-3a,4,5,6-tetrahydropyrrolo[1,2-c][1,3,2]oxazaborole;tribromoalumane 作用下， 以 二氯甲烷 、 甲苯 、 二溴甲烷 为溶剂， 反应 3.0h， 以95%的产率得到(1R,2S,4S)-2,2,2-trifluoroethyl 3-methylenebicyclo[2.2.1]hept-5-ene-2-carboxylate
  参考文献：
  名称：

  Enantioselective Pathway for the Synthesis of Laurenditerpenol

  摘要：

  Simple enantioselective routes to the two key intermediates shown above (at center) for the synthesis of laurenditerpenol have been developed using a Diels-Alder step and the same catalyst system for each.

  DOI：

  10.1021/ol1004802
• 作为产物：
  描述：

  2,2,2-三氟乙醇 、 3-丁炔酸 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.08h， 以20%的产率得到2,2,2-trifluoroethyl 2,3-butadienoate
  参考文献：
  名称：

  Catalytic Enantioselective Allenoate–Alkene [2 + 2] Cycloadditions

  摘要：

  Catalytic enantioselective [2 + 2] cycloadditions between allenoates and alkenes is disclosed. The method functions well for a variety of alkenes, and the products are generated with excellent levels of enantioselectivity. One of the most significant aspects of the present method is that unactivated alkenes are suitable substrates for this method, which is distinctly different from nearly all other catalytic enantioselective [2 + 2] cycloaddition methods.

  DOI：

  10.1021/jacs.5b00563

文献信息

• Allenoates in Enantioselective [2+2] Cycloadditions: From a Mechanistic Curiosity to a Stereospecific Transformation
  作者：Johannes. M. Wahl、Michael L. Conner、M. Kevin Brown

  DOI：10.1021/jacs.8b10008

  日期：2018.11.21

  selectivity, a detailed mechanistic investigation was conducted. Herein, two competing reaction pathways are proposed, which operate simultaneously and funnel the alkenes to the same axially chiral cyclobutanes. In agreement with the Woodward-Hoffmann rules, this mechanistic curiosity can be rationalized through a unique symmetry operation that was elucidated by deuteration experiments. In the case of 1,1-diarylalkenes

  新型催化剂-烯丙酸酯对的鉴定允许α-甲基苯乙烯的对映选择性[2+2]环加成。为了了解选择性的起源，进行了详细的机械研究。在此，提出了两种竞争性反应途径，它们同时操作并将烯烃漏斗为相同的轴向手性环丁烷。与伍德沃德-霍夫曼规则一致，这种机械好奇心可以通过氘化实验阐明的独特对称操作来合理化。在 1,1-二芳基烯烃的情况下，催化剂和烯烃之间的远距离通讯是通过电子性质和构象的细微改变来实现的。在这种情况下，哈米特的一项研究为协调机制提供了进一步的可信度。因此，扩展范围的探索，
• Phosphine-Catalyzed Synthesis of 1,3-Dioxan-4-ylidenes
  作者：Xue-Feng Zhu、Christopher E. Henry、Jay Wang、Travis Dudding、Ohyun Kwon

  DOI：10.1021/ol050203y

  日期：2005.3.1

  A phosphine-catalyzed reaction of an allenoate with aldehydes furnished (2,6-diaryl-[1,3]dioxan-4-ylidene)-acetates 4 in excellent to moderate yields with complete diastereoselectivity and high E/Z-selectivities. Upon removal of the acetal functionality in this domino reaction product 4, delta-hydroxy-beta-ketoester 11 was obtained. The reported vinylphosphonium-based approach provides a new way to achieve a synthesis of 6-hydroxy-beta-ketoesters that differs from the classical dianion-based approach.
• Enantioselective Pathway for the Synthesis of Laurenditerpenol
  作者：Santanu Mukherjee、Alex P. Scopton、E. J. Corey

  DOI：10.1021/ol1004802

  日期：2010.4.16

  Simple enantioselective routes to the two key intermediates shown above (at center) for the synthesis of laurenditerpenol have been developed using a Diels-Alder step and the same catalyst system for each.
• Catalytic Enantioselective Allenoate–Alkene [2 + 2] Cycloadditions
  作者：Michael L. Conner、Yao Xu、M. Kevin Brown

  DOI：10.1021/jacs.5b00563

  日期：2015.3.18

  Catalytic enantioselective [2 + 2] cycloadditions between allenoates and alkenes is disclosed. The method functions well for a variety of alkenes, and the products are generated with excellent levels of enantioselectivity. One of the most significant aspects of the present method is that unactivated alkenes are suitable substrates for this method, which is distinctly different from nearly all other catalytic enantioselective [2 + 2] cycloaddition methods.