1-(3-hydroxy-1-propynyl)-2-iodobenzene | 176384-79-5

• 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-(3-hydroxy-1-propynyl)-2-iodobenzene
• 英文别名: 3-(2-iodophenyl)-2-propyn-1-ol；3-(2-Iodo-phenyl)-prop-2-yn-1-ol；3-(2-iodophenyl)prop-2-yn-1-ol
• CAS: 176384-79-5
• 化学式: C₉H₇IO
• 分子量: 258.058
• InChiKey: DQNUSYKAAOXIGT-UHFFFAOYSA-N

物化性质

• 沸点：
  320.5±27.0 °C(Predicted)
• 密度：
  1.84±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 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：

  1-(3-hydroxy-1-propynyl)-2-iodobenzene 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 3-[2-(2-Trimethylsilylethynyl)phenyl]prop-2-ynyl methanesulfonate
  参考文献：
  名称：

  Synthesis of Indeno-Fused Derivatives of Quinolizinium Salts, Imidazo[1,2-a]pyridine, Pyrido[1,2-a]indole, and 4H-Quinolizin-4-one via Benzannulated Enyne−Allenes

  摘要：

  [GRAPHICS]The benzannulated enediynyl propargylic alcohol 8 was prepared from 1-bromo-2-iodobenzene by two consecutive Sonogashira cross-coupling reactions. The subsequent transformation to mesylate 9 followed by treatment with 4-substituted pyridines 10 then furnished the benzannulated enediynes 11. On exposure of 11 to triethylamine, the indeno-fused quinolizinium salts 15 were produced in quantitative yield. Presumably the reaction proceeded through a 1,3-prototropic rearrangement to form the benzannulated enyne-allenes 12, which then underwent either a concerted Diels-Alder reaction or a two-step process involving a Schmittel cyclization reaction to form biradical 13 followed by an intramolecular radical-radical coupling to afford 14. A subsequent prototropic rearrangement then produced 15. Similarly, 21a and 21b were produced from 19a and 19b, respectively. The use of the Sonogashira reaction for cross-coupling between 1-iodo-2-(phenylethynyl)benzene (7) and 1-(2-propynyl)-1H-imidazole (25) followed by treatment of the resulting adduct with potassium tertbutoxide gave the indeno-fused imidazo[1,2-a]pyridine 24 in 98% yield. Similarly, the indeno-fused pyrido[1,2-a]indole 32 and 4H-quinolizin-4-one 35 were obtained by starting from 7 for cross-coupling with 1-(2-propynyl)-1H-indole (30) and 1-(2-propynyl)-2(1H)-pyridinone (33), respectively, followed by treatment with potassium tent-butoxide.

  DOI：

  10.1021/jo0505730
• 作为产物：
  描述：

  2-(3-(2-tetrahydropyranyloxy)-1-propynyl)-1-iodobenzene 在 4-甲基苯磺酸吡啶 作用下， 以 乙醇 为溶剂， 反应 4.0h， 以90%的产率得到1-(3-hydroxy-1-propynyl)-2-iodobenzene
  参考文献：
  名称：

  串联自由基环化法从烯烯对映体合成角熔融芳烃。

  摘要：

  让“小号得到自由基：朝向的通用合成途径有角度的邻位-融合的聚芳族[4]由芳基链烯基N-取代的环状烯二炔起始helicenes被描述（参见方案; DMSO =二甲亚砜，NS = 4-硝基苯磺酰基）。该过程涉及Bergman环化（BC），这是前所未有的串联自由基反应的关键步骤。

  DOI：

  10.1002/anie.201103318

文献信息

• Gold‐Catalyzed Aminoaromatizations of 1,2‐Bis(alkynyl)benzenes with Anthranils to Yield 1‐Amino‐2‐napthaldehyde Products
  作者：Yashwant Bhaskar Pandit、Rai‐Shung Liu

  DOI：10.1002/adsc.202000591

  日期：2020.8.4

  Gold‐catalyzed aminoaromatizations of 1,n‐diynes with anthranils afforded 1‐amino‐2‐napthaldehyde derivatives efficiently. In this reaction sequence, anthranils preferably attack at gold‐coordinated prop‐3‐yn‐1‐ols to generate α‐imino gold carbenes that enable subsequent cyclizations with the other alkynes. Chemical functionalizations of the resulting 1‐amino‐2‐napthaldehydes are presented to manifest

  1，n-二炔与蒽的金催化氨基芳构化可有效地提供1-氨基-2-萘甲醛衍生物。在该反应顺序中，蒽优选攻击金配位的prop-3-yn-1-ol，生成α-亚氨基金卡宾，随后与其他炔烃环化。本文介绍了所得的1-氨基-2-萘甲醛的化学官能团，以证明这些反应的合成效用。
• Catalytic Enantioselective Synthesis of Chiral Tetraphenylenes: Consecutive Inter- and Intramolecular Cycloadditions of Two Triynes
  作者：Takanori Shibata、Tatsuya Chiba、Hiroyuki Hirashima、Yasunori Ueno、Kohei Endo

  DOI：10.1002/anie.200903715

  日期：2009.10.12

  Triynes having a phenylene‐bridged 1,5‐diyne moiety were transformed into substituted tetraphenylenes by the title sequence. A cationic Rh–ligand species catalyzed this highly enantioselective reaction. This protocol is a new and easy approach to the construction of the tetraphenylene skeleton and enables an efficient asymmetric synthesis (see scheme; R=H; Z=NTs, C(CO2Me)2, O).

  具有亚苯基桥接的1,5-二炔部分的三炔通过标题序列转化为取代的四亚苯基。阳离子Rh-配体物种催化了这种高度对映选择性的反应。该协议是一种构造四亚苯基骨架的新方法，可轻松实现高效的不对称合成（请参见方案； R = H； Z = NTs，C（CO 2 Me）2，O）。
• Palladium-Catalyzed Multicomponent Reaction (MCR) of Propargylic Carbonates with Isocyanides
  作者：Jianwen Peng、Yang Gao、Weigao Hu、Yinglan Gao、Miao Hu、Wanqing Wu、Yanwei Ren、Huanfeng Jiang

  DOI：10.1021/acs.orglett.6b02999

  日期：2016.11.18

  A palladium-catalyzed multicomponent reaction (MCR) of propargylic carbonates with isocyanides is reported. Remarkably, the orderly insertion of isocyanides affords two types of valuable N-heterocyclic products (Z)-6-imino-4,6-dihydro-1H-furo[3,4-b]pyrrol-2-amines and (E)-5-iminopyrrolones in high yields. Systematic analysis of the reaction conditions indicates that the selectivity of these N-heterocyclic

  报道了炔丙基碳酸酯与异氰酸酯的钯催化的多组分反应（MCR）。值得注意的是，有序插入异氰酸酯可提供两种有价值的N-杂环产物（Z）-6-亚氨基-4,6-二氢-1 H-呋喃[3,4- b ]吡咯-2-胺和（E） -5-亚氨基吡咯烷酮产量高。反应条件的系统分析表明，这些N-杂环产物的选择性可以通过配体和温度控制。
• Photocatalyzed Diastereoselective Isomerization of Cinnamyl Chlorides to Cyclopropanes
  作者：Bin Xu、Ludovic Troian-Gautier、Ryan Dykstra、Robert T. Martin、Osvaldo Gutierrez、Uttam K. Tambar

  DOI：10.1021/jacs.0c00147

  日期：2020.4.1

  Endergonic isomerizations are thermodynamically unfavored processes that are difficult to realize under thermal conditions. We report a photocatalytic diastereoselective isomerization of acyclic cinnamyl chlorides to strained cyclopropanes. Quantum mechanical calculations (uM06-2X and DLPNO), including TD-DFT calculations, and experimental studies provide evidence for the energy transfer from an iridium

  Endergonic 异构化是热力学上不利的过程，在热条件下难以实现。我们报告了无环肉桂酰氯到应变环丙烷的光催化非对映选择性异构化。量子力学计算（uM06-2X 和 DLPNO），包括 TD-DFT 计算和实验研究为能量从铱光催化剂转移到烯丙基氯化物底物，然后是 C-Cl 均裂提供了证据。随后的 Cl• 自由基迁移形成局部三重 1,3-双自由基中间体，在系统间交叉后，进行闭环以形成所需的产物。温和的反应条件与广泛的官能团兼容，以高产率和非对映选择性生成氯环丙烷。通过添加催化量的镍络合物开发了一种更有效的工艺，我们提出了这种助催化剂的新作用，以回收反应过程中产生的烯丙基氯副产物。该反应也显示为立体收敛的，因为肉桂酰氯的 E/Z 混合物以高非对映选择性提供抗氯环丙烷产物。我们预计，使用可见光活化的光催化剂转化底物与过渡金属催化剂相结合，将副产物循环回催化循环，将为发现新的反应性提供独特的机会。
• Tandem Enyne Allene−Radical Cyclization:  Low-Temperature Approaches to Benz[<i>e</i>]indene and Indene Compounds
  作者：Janet Wisniewski Grissom、Detlef Klingberg、Dahai Huang、Brian J. Slattery

  DOI：10.1021/jo961049j

  日期：1997.2.1

  multicyclic compounds using the tandem enediyne-radical cyclization, we have developed the tandem enyne allene-radical cyclization which proceeds at temperatures as low as 37 degrees C. The reactions were carried out using three different methods for the preparation of the enyne allenes. The first method involved the [3,3] sigmatropic rearrangement of an enediyne followed by a tandem enyne allene-radical

  为了降低使用串联烯二炔自由基环化制备多环化合物所需的温度，我们开发了串联烯炔丙二烯自由基环化反应，该反应在低至37摄氏度的温度下进行。反应使用三种不同的方法进行用于制备烯炔异戊烯。第一种方法涉及烯二炔的[3,3]σ重排，然后是串联烯炔-异戊二烯-自由基环化。此反应可以通过热解（150摄氏度）或通过AgBF（4）重排，然后在75摄氏度加热来实现。第二种技术是在-78摄氏度下利用烯键的[2,3]σ位移，然后在37或75摄氏度下进行串联环化反应，具体取决于底物。