2-[(triisopropylsilyl)ethynyl]phenol | 1062451-35-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 2-[(triisopropylsilyl)ethynyl]phenol
• 英文别名: 2-[2-Tri(propan-2-yl)silylethynyl]phenol
• CAS: 1062451-35-7
• 化学式: C₁₇H₂₆OSi
• 分子量: 274.478
• InChiKey: ZUIMTGHBNKQRQB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.96
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-[(triisopropylsilyl)ethynyl]phenol 在 (acetylacetonato)dicarbonylrhodium (l) 、 水 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以30%的产率得到2-tri-isopropylsilylbenzofuran
  参考文献：
  名称：

  多米诺铑（I）催化的反应可有效合成取代的苯并呋喃和吲哚

  摘要：

  铑（I）催化剂促进邻炔基苯酚和苯胺转化为相应的苯并[ b ]呋喃和吲哚。假定该反应通过过渡的3-铑杂环中间体进行，该中间体可以用合适的亲电试剂捕获以得到多取代的杂环。在单取代的吸电子亲电体的情况下，与Heck-Mizoroki反应相比，可以获得优异的收率和选择性。在2-炔基吡啶亲电试剂的情况下，形成新的2-（苯并呋喃-3-基）乙烯基吡啶。

  DOI：

  10.1016/j.tet.2010.05.106
• 作为产物：
  描述：

  在 盐酸 、 水 作用下， 以 丙酮 为溶剂， 反应 3.0h， 以76%的产率得到2-[(triisopropylsilyl)ethynyl]phenol
  参考文献：
  名称：

  Stereoselective Synthesis of the Rocaglamide Skeleton via a Silyl Vinylketene Formation/[4 + 1] Annulation Sequence

  摘要：

  The tricyclic core of the cyclopentabenzofurans has been prepared in an efficient and stereoselective manner utilizing an intramolecular silyl vinylketene formation/[4 + 1] annulation sequence. This novel approach affords the ABC ring system where the adjacent phenyl and aryl substituents of the C ring have the required cis relationship.

  DOI：

  10.1021/ol801435j

文献信息

• Thermal [2 + 2]-cycloaddition between silylalkynes and allenylphenols followed by the nucleophilic addition of water: metal-free and economical synthesis of arylcyclobutenals
  作者：Shohei Ohno、Ramon Francisco Avena、Hiroshi Aoyama、Hiromichi Fujioka、Mitsuhiro Arisawa

  DOI：10.1039/c9gc04184b

  日期：——

  A novel thermal [2 + 2]-cycloaddition between silylalkynes and allenylphenols to form a cyclobutachromene intermediate, followed by the nucleophilic addition of water to yield functionalized arylcyclobutenals.

  一种新颖的热[2 + 2]-环加成反应，通过硅烯炔和烯丙基酚之间的反应形成环丁基色素烯中间体，随后通过水的亲核加成得到官能化芳基环丁酮。
• Ni-Catalyzed Cycloisomerization between 3-Phenoxy Acrylic Acid Derivatives and Alkynes via Intramolecular Cleavage and Formation of the C–O Bond To Give 2,3-Disubstituted Benzofurans
  作者：Shohei Ohno、Jiawei Qiu、Ray Miyazaki、Hiroshi Aoyama、Kenichi Murai、Jun-ya Hasegawa、Mitsuhiro Arisawa

  DOI：10.1021/acs.orglett.9b03170

  日期：2019.10.18

  based on transition-metal-catalyzed C-O bond cleavage have attracted much attention as a new synthetic method. Until now, several intermolecular reactions via C-O bond cleavage of aryl ethers, alkenyl ethers, esters, and others have been reported. Here we report an unprecedented C-O bond cleavage of 3-phenoxy acrylic acid derivatives, followed by intramolecular C-O bond formation with alkynes. This reaction

  作为一种新的合成方法，基于过渡金属催化的CO键断裂的反应引起了人们的广泛关注。迄今为止，已经报道了通过芳族醚，烯基醚，酯等的CO键裂解的几种分子间反应。在这里，我们报告了前所未有的3-苯氧基丙烯酸衍生物的CO键断裂，随后与炔烃分子内形成CO键。该反应得到分别在2-和3-位具有有用的官能团-甲硅烷基取代基和丙烯酸衍生物的2，3-二取代的苯并呋喃。该报告还描述了对该机制的理论（DFT）见解。
• Rhodium-Catalyzed Cycloisomerization of 2-Silylethynyl Phenols and Anilines via 1,2-Silicon Migration
  作者：Hiroshi Kanno、Kyosuke Nakamura、Keiichi Noguchi、Yu Shibata、Ken Tanaka

  DOI：10.1021/acs.orglett.6b00529

  日期：2016.4.1

  It has been established that a cationic rhodium(I)/BINAP complex catalyzes the cycloisomerization of 2-silylethynylphenols, leading to 3-silylbenzofurans, via 1,2-silicon migration. Similarly, the cycloisomerization of 2-silylethynylanilines, leading to 3-silylindoles, via 1,2-silicon migration was catalyzed by a cationic rhodium(I)/H8–BINAP complex.

  已经确定，阳离子铑（I）/ BINAP络合物催化2-甲硅烷基乙炔基苯酚的环异构化，通过1，2-硅迁移导致3-甲硅烷基苯并呋喃。同样，阳离子铑（I）/ H 8 -BINAP络合物催化通过1,2-硅迁移的2-甲硅烷基乙炔基苯胺的环异构化，生成3-甲硅烷基。
• Improved Photostability of a Cu ^I Complex by Macrocyclization of the Phenanthroline Ligands
  作者：Thomas Brandl、Christoph Kerzig、Loïc Le Pleux、Alessandro Prescimone、Oliver S. Wenger、Marcel Mayor

  DOI：10.1002/chem.201904754

  日期：2020.3.9

  role. While copper(I)-bis(diimine) complexes [CuI (L)2 ]+ are considered as potent substitutes for [RuII (bpy)3 ]2+ , they exhibit limited structural integrity as ligand loss by substitution can occur. In this article, we present a new concept to stabilize copper bis(phenanthroline) complexes by macrocyclization of the ligands which are preorganized around the CuI ion. Using oxidative Hay acetylene

  用于将太阳能转化为电能和燃料的分子材料的开发是最活跃的研究领域之一，其中光吸收剂起着关键作用。尽管铜（I）-双（二亚胺）络合物[CuI（L）2] +被认为是[RuII（bpy）3] 2+的有效替代物，但它们的结构完整性有限，因为配体会因取代而丢失。在本文中，我们提出了一个新概念，可通过对围绕CuI离子进行预组织的配体进行大环化来稳定铜双（菲咯啉）配合物。使用氧化Hay乙炔均偶联条件，制备并分析了几种具有不同桥长的CuI配合物。评估吸收和发射特性；值得庆幸的是，由于灵活的1，
• Mild and Efficient Ir(III)-Catalyzed Direct C–H Alkynylation of <i>N</i>-Phenoxyacetamides with Terminal Alkyne
  作者：Jie Zhou、Jingjing Shi、Zisong Qi、Xingwei Li、H. Eric Xu、Wei Yi

  DOI：10.1021/acscatal.5b01571

  日期：2015.11.6

  Ir(III)-catalyzed direct C-H alkynylation of arenes has been developed using commercially available TIPS-acetylene as an efficient alkynylating reagent, where O-NHAc was employed as an autocleavable oxidizing-directing group (ODG(auto)), thus giving rise to ortho-alkynylated phenols under mild reaction conditions in a highly efficient and redox-neutral manner. The reaction proceeded with high regioselectivity and broad substrate/functional group (FG) tolerance. The synthetic application of the products has been briefly exemplified. Preliminary mechanistic studies have been conducted, and a five-membered iridacycle has also been identified as a key intermediate.