1-[2-(4-Methylphenyl)sulfonylethynyl]-3,5-bis(trifluoromethyl)benzene | 1374637-66-7

• 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-[2-(4-Methylphenyl)sulfonylethynyl]-3,5-bis(trifluoromethyl)benzene
• 英文别名: 1-[2-(4-methylphenyl)sulfonylethynyl]-3,5-bis(trifluoromethyl)benzene
• CAS: 1374637-66-7
• 化学式: C₁₇H₁₀F₆O₂S
• 分子量: 392.322
• InChiKey: SSWBBYRWOPYDJC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1-[2-(4-Methylphenyl)sulfonylethynyl]-3,5-bis(trifluoromethyl)benzene 、 (4-trifluoromethylphenyl)lithium 以 四氢呋喃 为溶剂， 反应 0.08h， 以81%的产率得到1,3-bis(trifluoromethyl)-5-[(4-trifluoromethylphenyl)ethynyl]benzene
  参考文献：
  名称：

  Arylsulfonylacetylenes as Alkynylating Reagents

  摘要：

  The unexpected anti-Michael addition of RLi to -substituted sulfonylacetylenes, followed by in situ elimination of the ion sulfinate, allows the alkynylation of C(sp(2)) and C(sp(3)). Aryl and heteroaryl acetylenes, enynes, and mono and dialkyl alkynes can be obtained in very high yields under very mild conditions, avoiding the use of transition metals as catalysts and, in many cases, haloderivatives as starting materials. Furthermore, the use of lithium 2-p-tolylsulfinyl benzylcarbanions as nucleophiles of these reactions allows their stereocontrolled alkynylation, affording enantiomerically pure alkynes or enantioenriched allenes depending on the protonating agent (NH4Cl or H2O).

  DOI：

  10.1080/10426507.2012.748054

文献信息

• Arylsulfonylacetylenes as Alkynylating Reagents of C sp 2H Bonds Activated with Lithium Bases
  作者：José Luis García Ruano、José Alemán、Leyre Marzo、Cuauhtémoc Alvarado、Mariola Tortosa、Sergio Díaz-Tendero、Alberto Fraile

  DOI：10.1002/anie.201107821

  日期：2012.3.12

  strategy for the synthesis of a wide variety of alkynyl derivatives by the reaction of substituted arylsulfonylacetylenes with organolithium species is described (see scheme). The high yields, the simplicity of the experimental procedure, the broad scope of this reaction, and the formation of CspC bonds without using transition metals are the main features of this methodology.

  变色龙：描述了通过取代的芳基磺酰基乙炔与有机锂物质反应合成多种炔基衍生物的新策略（参见方案）。高产量，的实验程序的简单性，该反应的宽范围，和C的形成SP  Ç键不使用的过渡金属是这种方法的主要特征。
• Expanding the Scope of Arylsulfonylacetylenes as Alkynylating Reagents and Mechanistic Insights in the Formation of Csp²Csp and Csp³Csp Bonds from Organolithiums
  作者：José Luis García Ruano、José Alemán、Leyre Marzo、Cuauhtémoc Alvarado、Mariola Tortosa、Sergio Díaz‐Tendero、Alberto Fraile

  DOI：10.1002/chem.201200939

  日期：2012.7.2

  We describe the unexpected behavior of the arylsulfonylacetylenes, which suffer an “anti‐Michael” addition of organolithiums producing their alkynylation under very mild conditions. The broad scope, excellent yields, and simplicity of the experimental procedure are the main features of this methodology. A rational explanation of all these results can be achieved by theoretical calculations, which suggest

  我们描述了芳基磺酰基乙炔的出乎意料的行为，芳基磺酰基乙炔在非常温和的条件下会遭受“反迈克尔”加成的有机锂的作用，从而产生炔基化反应。这种方法的主要特点是范围广，产率高，实验步骤简单。所有这些结果的合理解释可以通过理论计算来实现，这表明有机锂与亲电试剂的缔合是其分子内攻击的前一步，并且是观察到的对取代的磺酰基乙炔的意外“反迈克尔”反应的原因。
• Asymmetric Synthesis of Secondary and Tertiary Propargylic Alcohols by Umpolung of Acetylenic Sulfones and <i>ortho</i>-Sulfinyl Carbanions
  作者：Ricardo I. Rodríguez、Elsie Ramírez、Francisco Yuste、Rubén Sánchez-Obregón、José Alemán

  DOI：10.1021/acs.joc.7b02887

  日期：2018.2.16

  scope of this alkynylation reaction is also discussed. Moreover, the development of a new approach for the synthesis of optically active tertiary benzylpropargyl alcohols is described, discussing the possible stereocourse of the reaction so as the influence of the ether 18-crown-6 and steric importance of acetylenic substituent.

  由不对称加成的非对映体富集的仲苄基炔丙基醇的生成邻位通过形成CSP-CSP的-sulfinylbenzyl碳负离子至sulfonylacetylene衍生物3键进行说明。该反应通过不寻常的邻亚磺酰基苄基碳负离子的α-攻击（抗迈克尔加成反应）进行，然后消除芳基磺酰基部分。还讨论了该炔基化反应的范围。此外，描述了合成光学活性的叔苄基丙炔醇的新方法的发展，讨论了反应的可能立体过程，如醚18-crown-6的影响和炔基取代基的空间重要性。
• Synthesis of Alkyl-Ynol-Ethers by “Anti-Michael Addition” of Metal Alkoxides to β-Substituted Alkynylsulfones
  作者：Leyre Marzo、Alejandro Parra、María Frías、José Alemán、José Luis García Ruano

  DOI：10.1002/ejoc.201300395

  日期：2013.7

  alkoxides with β-substituted 2-(p-tolylsulfonyl)acetylenes, involving an anti-Michael addition reaction followed by the in situ elimination of the sulfonyl moiety, provides a direct method for the synthesis of alkyl alkynyl ethers bearing aryl or TIPS groups joined to the triple bond. Arylalkynyl ethers derived from primary alkoxides are in situ hydrolyzed into arylacetic esters.

  金属醇盐与 β-取代的 2-（对甲苯磺酰基）乙炔反应，包括反迈克尔加成反应，然后原位消除磺酰基部分，为合成带有芳基或芳基的烷基炔基醚提供了一种直接方法。 TIPS 基团加入了三键。衍生自伯醇盐的芳炔基醚原位水解成芳基乙酸酯。
• Arylsulfonylacetylenes as Alkynylating Reagents
  作者：Leyre Marzo、José Alemán、José Luis García Ruano

  DOI：10.1080/10426507.2012.748054

  日期：2013.4.1

  The unexpected anti-Michael addition of RLi to -substituted sulfonylacetylenes, followed by in situ elimination of the ion sulfinate, allows the alkynylation of C(sp(2)) and C(sp(3)). Aryl and heteroaryl acetylenes, enynes, and mono and dialkyl alkynes can be obtained in very high yields under very mild conditions, avoiding the use of transition metals as catalysts and, in many cases, haloderivatives as starting materials. Furthermore, the use of lithium 2-p-tolylsulfinyl benzylcarbanions as nucleophiles of these reactions allows their stereocontrolled alkynylation, affording enantiomerically pure alkynes or enantioenriched allenes depending on the protonating agent (NH4Cl or H2O).