(((2-bromophenyl)thio)ethynyl)triisopropylsilane | 1443746-53-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (((2-bromophenyl)thio)ethynyl)triisopropylsilane
• 英文别名: 2-(2-Bromophenyl)sulfanylethynyl-tri(propan-2-yl)silane
• CAS: 1443746-53-9
• 化学式: C₁₇H₂₅BrSSi
• 分子量: 369.441
• InChiKey: IKMVWFQMHLFSKA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.72
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  三异丙基氯硅烷 在 正丁基锂 、 三氟甲磺酸三甲基硅酯 、 四甲基胍 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 反应 1.99h， 生成 (((2-bromophenyl)thio)ethynyl)triisopropylsilane
  参考文献：
  名称：

  A Highly Chemoselective and Practical Alkynylation of Thiols

  摘要：

  A thiol-alkynylation procedure utilizing the hypervalent iodine alkyne transfer reagent TIPS-ethynyl-benziodoxolone has been developed. This scalable reaction proceeds in five minutes at room temperature in an open flask using commercially available reagents. The scope of the reaction is broad, with a variety of phenolic, benzylic, heterocyclic, and aliphatic thiols undergoing alkynylation in excellent yield. The method is highly chemoselective as a vast array of functional groups are tolerated. The utility of the thiol-alkynylation in postsynthetic elaboration has been demonstrated through the facile installment of a fluorophore tag on a cysteine-containing peptide.

  DOI：

  10.1021/ja4044196

文献信息

• Tosyloxybenziodoxolone: A Platform for Performing the Umpolung of Alkynes in One-Pot Transformations
  作者：Julien Borrel、Jerome Waser

  DOI：10.1021/acs.orglett.1c03771

  日期：2022.1.14

  Ethynylbenziodoxolones (EBXs) are commonly encountered reagents for the electrophilic alkynylation of nucleophiles. Herein, we report a one-pot, two-step process for EBX generation and their direct application in substrate functionalization. Our approach enables us to bypass the originally mandatory isolation and purification of the reagents, resulting in a more efficient synthesis. We could apply

  Ethynylbenziodoxolones (EBXs) 是亲核试剂亲电炔基化的常用试剂​​。在这里，我们报告了用于 EBX 生成的一锅两步工艺及其在基板功能化中的直接应用。我们的方法使我们能够绕过最初强制性的试剂分离和纯化，从而实现更有效的合成。我们可以将此过程应用于涉及双电子和单电子亲核试剂的七种不同转化，以获得多种炔基化产物。
• Ethynylbenziodazolones (EBZ) as Electrophilic Alkynylation Reagents for the Highly Enantioselective Copper‐Catalyzed Oxyalkynylation of Diazo Compounds
  作者：Durga Prasad Hari、Lionel Schouwey、Verity Barber、Rosario Scopelliti、Farzaneh Fadaei‐Tirani、Jerome Waser

  DOI：10.1002/chem.201900950

  日期：2019.7.17

  radicals and nucleophiles, yet they present limited possibilities for further structure and reactivity modification. Herein, the first synthesis is reported for the corresponding ethynylbenziodazolone (EBZ) reagents, in which the oxygen atom in the iodoheterocycle is replaced by a nitrogen atom. The substituent on the nitrogen enables further fine‐tuning of the reagent structure and reactivity. EBZ reagents

  乙炔基苯并恶唑（EBX）环状高价碘试剂现已确立为自由基和亲核试剂烷基化的试剂，但它们为进一步的结构和反应性修饰提供了有限的可能性。在此，报道了相应乙炔基苯并偶氮酮（EBZ）试剂的第一次合成，其中碘杂环中的氧原子被氮原子取代。氮上的取代基可进一步微调试剂的结构和反应性。EBZ试剂可通过一步步骤轻松地从相应的苯甲酰胺中获得，并具有与EBX试剂相当的反应性。特别是，它们被用于重氮化合物的不对称铜催化的氧炔基化反应中，
• Structure and Reactivity of N‐Heterocyclic Alkynyl Hypervalent Iodine Reagents
  作者：Eliott Le Du、Thibaut Duhail、Matthew D. Wodrich、Rosario Scopelliti、Farzaneh Fadaei‐Tirani、Elsa Anselmi、Emmanuel Magnier、Jerome Waser

  DOI：10.1002/chem.202101475

  日期：2021.7.26

  Ethynylbenziodoxol(on)e (EBX) cyclic hypervalent iodine reagents have become popular reagents for the alkynylation of radicals and nucleophiles, but only offer limited possibilities for further structure and reactivity fine-tuning. Herein, the synthesis of new N-heterocyclic hypervalent iodine reagents with increased structural flexibility based on amide, amidine and sulfoximine scaffolds is reported

  乙炔苯并氧杂环戊烯 (EBX) 环状高价碘试剂已成为自由基和亲核试剂炔基化的常用试剂​​，但仅为进一步结构和反应性微调提供有限的可能性。在此，报道了基于酰胺、脒和亚砜亚胺支架的新型N-杂环高价碘试剂的合成，该试剂具有增加的结构灵活性。报告了试剂的固态结构，并且对 I−C炔键长度的分析允许评估不同取代基的反式效应。由 DFT 计算得出的试剂分子静电势 (MEP) 图揭示了磺酰胺基化合物不太明显的 σ 孔区域。大多数试剂在β-酮酯的炔基化反应中反应良好。硫醇的炔基化提供了更多的可变产率，具有更强σ-空穴的化合物反应更好。在金属介导的转化中，与 O 基 EBX 试剂相比，N-杂环高价碘试剂的结果较差。
• Radical Alkynylthiolation with Visible-Light-Sensitive S-Alkynylthio Sulfonates
  作者：Yaonan Xue、Qirui Dong、Jiarui Chen、Hang Gao、Honghong Chang、Jun Tian、Wen-Chao Gao

  DOI：10.1021/acs.orglett.4c02259

  日期：2024.8.23

  systems and radical coupling with diazonium salts under photocatalyst-free conditions. This strategy features a broad substrate scope, high regioselectivity, excellent tolerance of functional groups, and the late-stage modification of drugs. Experimental and theoretical mechanistic investigations gave reasonable insight into the photolysis of S-alkynylthio sulfonates and C–S bond formation.

  开发了一种新型S-炔基硫代磺酸盐，可在可见光照射下直接活化，用于在无光催化剂条件下进行多键体系的自由基加成以及与重氮盐的自由基偶联。该策略具有底物范围广、区域选择性高、官能团耐受性好以及药物后期修饰等特点。实验和理论机理研究为S-炔硫基磺酸盐的光解和 C-S 键的形成提供了合理的见解。