((4-(tert-butyl)phenyl)ethynyl)(trifluoromethyl)sulfane | 1388753-55-6

• 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: ((4-(tert-butyl)phenyl)ethynyl)(trifluoromethyl)sulfane
• 英文别名: 1-Tert-butyl-4-[2-(trifluoromethylsulfanyl)ethynyl]benzene；1-tert-butyl-4-[2-(trifluoromethylsulfanyl)ethynyl]benzene
• CAS: 1388753-55-6
• 化学式: C₁₃H₁₃F₃S
• 分子量: 258.307
• InChiKey: HZCNCIUIZRLOJZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  异戊醛 、 ((4-(tert-butyl)phenyl)ethynyl)(trifluoromethyl)sulfane 在 tetrakis(tetrabutylammonium)decatungstate(VI) 作用下， 以 水 、 乙腈 为溶剂， 以66 %的产率得到3-(4-(tert-butyl)phenyl)-4,4-dimethyl-2-((trifluoromethyl)thio)cyclopentan-1-one
  参考文献：
  名称：

  10.1002/anie.202407689

  摘要：

  A photocatalyzed formal (3+2) cycloaddition has been developed to construct original polysubstituted α‐SCF3 cyclopentanones in a regio‐ and diastereoselective manner. This building block approach leverages trifluoromethylthio alkynes and branched / linear aldehydes, as readily available reaction partners, in consecutive hydrogen atom transfers and C–C bond formations. Difluoromethylthio alkynes are also compatible subtrates. Furthermore, the potential for telescoped reaction starting from alcohols instead of aldehydes was demonstrated, as well as process automatization and scale‐up under continuous microflow conditions. This prompted density functional theory calculations to support a free radical‐mediated cascade hydrogen atom transfer process.

  DOI：

  10.1002/anie.202407689
• 作为产物：
  描述：

  4-叔-丁基苯基乙炔 、 (三氟甲基)三甲基硅烷 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 potassium fluoride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 以85%的产率得到((4-(tert-butyl)phenyl)ethynyl)(trifluoromethyl)sulfane
  参考文献：
  名称：

  CF3SiMe3和元素硫对末端炔烃的无金属氧化三氟甲硫基化反应

  摘要：

  已经开发出在室温下使用现成的 CF(3)SiMe(3) 和元素硫对末端炔烃进行无金属氧化三氟甲基硫醇化。该反应为制备具有广泛官能团的炔基三氟甲基硫化物提供了一种高效便捷的方法。初步调查显示元素硫代替空气充当氧化剂。

  DOI：

  10.1021/ja305801m

文献信息

• Structure–Reactivity Relationship of Trifluoromethanesulfenates: Discovery of an Electrophilic Trifluoromethylthiolating Reagent
  作者：Xinxin Shao、Chunfa Xu、Long Lu、Qilong Shen

  DOI：10.1021/jo502645m

  日期：2015.3.20

  A family of electrophilic trifluoromethanesulfenates was prepared. Structure–reactivity relationship studies showed that the substituted groups on the aryl ring of the trifluoromethylthiolating reagent did not have an obvious influence on their reactivities. A simplified electrophilic trifluoromethylthiolating reagent 1c was then identified that can react with a wide range of nucleophiles such as Grignard

  制备了亲电三氟甲烷亚磺酸盐家族。结构反应关系研究表明，三氟甲基硫醇化试剂的芳基环上的取代基对其反应活性没有明显影响。然后鉴定出一种简化的亲电子三氟甲基硫醇化试剂1c，它可以在温和的反应条件下与格氏试剂，芳基硼酸，炔烃，吲哚，β-酮酸酯，羟吲哚和亚磺酸钠等多种亲核试剂反应。在这些条件下可以耐受多种官能团。
• Difluorocarbene-based trifluoromethylthiolation of terminal alkynes
  作者：Guowen He、Yan-Hua Jiang、Xuan Xiao、Jin-Hong Lin、Xing Zheng、Ruo-Bing Du、Yu-Cai Cao、Ji-Chang Xiao

  DOI：10.1016/j.jfluchem.2019.109437

  日期：2020.2

  A large number of trifluoromethylthiolation methods have been developed, but a trifluoromethylthiolation reagent usually has to be used in these methods. Herein we describe a difluorocarbene-based trifluoromethylthiolation of terminal alkynes to construct a Csp-SCF3 bond catalysed by a copper complex. Ph3P+CF2CO2-/S8/F- was used as a reagent system to form the CF3S- anion, and the sequential formation

  已经开发了大量的三氟甲基硫醇化方法，但是在这些方法中通常必须使用三氟甲基硫醇化试剂。在本文中，我们描述了末端炔烃的基于二氟卡宾的三氟甲基硫醇化，以构建由铜配合物催化的Csp-SCF 3键。用Ph 3 P + CF 2 CO 2- / S 8 / F-作为试剂体系形成CF 3 S-阴离子，依次形成CF 2 = S，F-CF 2 S和C-SCF 3一步一步就可以实现纽带。
• Oxidative Trifluoromethylthiolation of Terminal Alkynes with AgSCF₃: A Convenient Approach to Alkynyl Trifluoromethyl Sulfides
  作者：Sheng-Qing Zhu、Xiu-Hua Xu、Feng-Ling Qing

  DOI：10.1002/ejoc.201402533

  日期：2014.7

  new method for the efficient synthesis of alkynyl trifluoromethyl sulfides was developed. By combining AgSCF3 and NCS in N,N-dimethylacetamide, an electrophilic active intermediate was produced, which was then treated with a variety of terminal alkynes to afford the corresponding trifluoromethanesulfenylated products in moderate to excellent yields.

  开发了一种高效合成炔基三氟甲基硫化物的新方法。通过在 N,N-二甲基乙酰胺中结合 AgSCF3 和 NCS，产生了亲电活性中间体，然后用各种末端炔烃处理，以中等至极好的收率提供相应的三氟甲磺酰化产物。
• Direct trifluoromethylthiolation of terminal alkynes mediated by a hypervalent trifluoromethylthio-iodine(iii) reagent; boosting effect of fluorinated alcohol
  作者：Yu-Xin Cheng、Xiao-Guang Yang、Feng-Huan Du、Chi Zhang

  DOI：10.1039/d4gc00622d

  日期：——

  The direct trifluoromethylthiolation of terminal alkynes is an important strategy for accessing CF3S-containing compounds. Herein, we report a direct trifluoromethylthiolation reaction of various terminal alkynes employing a new hypervalent trifluoromethylthio-iodine(III) reagent TFTI in a fluorinated alcohol, either 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) or perfluoro-tert-butanol (PFTB). The reaction

  末端炔烃的直接三氟甲硫基化是获得含CF 3 S化合物的重要策略。在此，我们报道了使用新型高价三氟甲硫基碘 ( III ) 试剂 TFTI 在氟化醇（1,1,1,3,3,3-六氟-2-丙醇 (HFIP)）中对各种末端炔烃进行直接三氟甲硫基化反应或全氟叔丁醇（PFTB）。基于实验和DFT计算提出了反应机理。 TFTI 的可持续性和 PFTB 的回收使得反应环境友好。而且，根据绿色化学指标评估和 EcoScale 评分，该协议被认为是绿色化学背景下的优秀协议。