2-三氟甲基苯硼酸新戊二醇酯 | 95753-22-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2-三氟甲基苯硼酸新戊二醇酯
• 英文名称: 5,5-dimethyl-2-(2-(trifluoromethyl)phenyl)-1,3,2-dioxaborinane
• 英文别名: 5,5-dimethyl-2-[2-(trifluoromethyl)phenyl]-1,3,2-dioxaborinane
• CAS: 95753-22-3
• 化学式: C₁₂H₁₄BF₃O₂
• 分子量: 258.048
• InChiKey: FWYOUBPQXPFVOP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.47
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  5

安全信息

• 危险性防范说明：
  P261,P264,P270,P271,P280,P301+P312,P302+P352,P304+P340,P305+P351+P338,P330,P332+P313,P337+P313,P362,P403+P233,P405,P501
• 危险性描述：
  H302,H315,H319,H335

反应信息

• 作为反应物：
  描述：

  2-三氟甲基苯硼酸新戊二醇酯 在 二氟化氢钾 作用下， 以 甲醇 、 水 为溶剂， 生成 potassium trifluoro(2-(trifluoromethyl)phenyl)borate
  参考文献：
  名称：

  Neopentylglycolborylation of ortho-Substituted Aryl Halides Catalyzed by NiCl₂-Based Mixed-Ligand Systems

  摘要：

  NiCl2-based mixed-ligand systems were shown to be very effective catalysts for the neopentylglycolborylation of aryl iodides, bromides, and chlorides bearing electron-rich and electron-deficient ortho-substituents. Although NiCl2-based single-ligand catalytic systems were able to mediate neopentylglycolborylation of selected substrates, they were not as effective for all substrates, highlighting the value of the mixed-ligand concept. Optimization of the Ni(II)-catalyzed neopentylglycolborylation of 2-iodoanisole and methyl 2-iodobenzoate demonstrated that, while the role of ligand and coligand in the conversion of Ni(II) precatalyst to Ni(0) active catalyst cannot be ignored, a mixed-ligand complex is likely present throughout the catalytic cycle. In addition, protodeborylation and hydrodehalogenation were demonstrated to be the predominant side reactions of borylation of ortho-substituted aryl halides containing the electron-deficient carboxylate substituents. Ni(II) complexes in the presence of H2O and Ni(0) are responsible for the catalysis of these side reactions.

  DOI：

  10.1021/jo101023t
• 作为产物：
  描述：

  邻溴三氟甲苯 、 neopentylglycolborane 在 1,1'-双(二苯基膦)二茂铁 、 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) 、 三乙胺 、 锌 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以85%的产率得到2-三氟甲基苯硼酸新戊二醇酯
  参考文献：
  名称：

  Zero-Valent Metals Accelerate the Neopentylglycolborylation of Aryl Halides Catalyzed by NiCl₂-Based Mixed-Ligand Systems

  摘要：

  The highly active mixed-ligand catalytic system NiCl2(dppp)/dppf combined with the reducing effect of zerovalent Zn and of other metals was used to demonstrate a method for the dramatic acceleration of the rate and for the enhancement of the yield of Ni-catalyzed neopentylglycolborylation of aryl halides A diversity of electron-rich and electron-deficient aryl iodides, bromides, and chlorides were efficiently neopentylglycolborylated, typically in 1 h or less This acceleration is particularly remarkable for the generally less reactive aryl bromides and chlorides and for all ortho-substituted aryl halides By accelerating the rate of borylation and reducing its reaction time to complete conversion, pathways leading to protodeborylated or hydrodehalogenated side products have a reduced impact on the outcome of the overall reaction Although Zn powder was the reducing agent of choice, compatibility of this technique with more readily recoverable Zn chips, as well as other metals such as Mn, Mg, Fe, Al, and Ca, has demonstrated the broad scope of this synthetic method

  DOI：

  10.1021/jo101718v

文献信息

• Silver(i)-catalyzed carboxylation of arylboronic esters with CO2
  作者：Xiao Zhang、Wen-Zhen Zhang、Ling-Long Shi、Chun-Xiao Guo、Ling-Ling Zhang、Xiao-Bing Lu

  DOI：10.1039/c2cc32045b

  日期：——

  A variety of arylboronic esters were efficiently carboxylated with CO2 using a simple AgOAc/PPh3 catalyst, affording the corresponding carboxylic acids in good yield. This simple and efficient silver(I) catalytic system showed wide functional group compatibility.

  多种芳基硼酸酯通过简单AgOAc/PPh3催化剂高效地与二氧化碳发生羧基化反应，生成相应的羧酸，产率良好。这一简单高效的银(I)催化体系表现出广泛的官能团兼容性。
• CH Activation by Amide Chelation Control: Ruthenium‐ Catalyzed Direct Synthesis of 2‐Aryl‐3‐furanamides
  作者：Yigang Zhao、Victor Snieckus

  DOI：10.1002/adsc.201400147

  日期：2014.5.5

  methodology for the synthesis of heterobiaryls by the ruthenium‐catalyzed CH activation/cross‐coupling of heterocyclic amides with aryl boroneopentylates is surveyed. From this survey, the highly regioselective reaction of furan‐3‐carboxamide to give 2‐aryl‐3‐furanamides is optimized and generalized in scope with respect to the aryl boroneopentylate coupling partners. Established thereby is a one‐step synthetic

  一种新的，催化方法由钌催化C中的合成heterobiaryls的 ħ活化调查杂环酰胺与芳基boroneopentylates交叉耦合/。从这项调查中，呋喃-3-羧酰胺产生2-芳基-3-呋喃酰胺的高度区域选择性反应在芳基硼戊酸酯基偶联偶合剂的范围内得到了优化和推广。从而建立是凌驾的广泛应用两步指向的一步法合成方法邻金属化（DOM）-Cross偶联反应涉及低温和强碱条件并且具有用于进一步的潜在邻和远程金属化化学。
• Beyond Directed <i>ortho</i> Metalation: Ru-Catalyzed C_Ar–O Activation/Cross-Coupling Reaction by Amide Chelation
  作者：Yigang Zhao、Victor Snieckus

  DOI：10.1021/ja503819x

  日期：2014.8.13

  Disclosed is a new, catalytic, and general methodology for the chemical synthesis of biaryl, heterobiaryl, and polyaryl molecules by the cross-coupling of o-methoxybenzamides with aryl boroneopentylates. The reaction is based on the activation of the unreactive C-OMe bond by the proximate amide directing group using catalytic RuH2(CO)(PPh3)3 conditions. A one-step, base-free coupling process is thereby

  公开了一种通过邻甲氧基苯甲酰胺与芳基硼戊酸酯的交叉偶联化学合成联芳基、杂联芳基和聚芳基分子的新的、催化的和通用的方法。该反应基于使用催化 RuH2(CO)(PPh3)3 条件通过邻近的酰胺导向基团激活非反应性 C-OMe 键。由此建立了一步、无碱偶联过程，它有可能取代有用的两步定向邻位金属化/交叉偶联反应，包括低温和强碱条件。高区域选择性、与 Suzuki-Miyaura 反应的正交性、操作简单、浪费最少和方便的放大使这些反应适合工业应用。
• <i>Ipso-</i>Borylation of Aryl Ethers via Ni-Catalyzed C–OMe Cleavage
  作者：Cayetana Zarate、Rubén Manzano、Ruben Martin

  DOI：10.1021/jacs.5b03955

  日期：2015.6.3

  A Ni-catalyzed ipso-borylation of aryl ethers via C(sp(2))-OMe and C(sp(3))-OMe Cleavage is described. The transformation is characterized by its wide substrate scope tinder mild conditions and an exquisite divergence in Site selectivity that can be easily switched by selecting the appropriate, boron reagent.
• Lauer, Manfred; Boehnke, Helmut; Grotstollen, Reiner, Chemische Berichte, 1985, vol. 118, # 1, p. 246 - 260
  作者：Lauer, Manfred、Boehnke, Helmut、Grotstollen, Reiner、Salehnia, Mohammad、Wulff, Guenter

  DOI：——

  日期：——