2-(4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenyl)acetonitrile

• 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: 2-(4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenyl)acetonitrile
• 英文别名: 5,5-dimethyl-2-(4-cyanomethylphenyl)-1,3,2-dioxaborinane；[4-(5,5-Dimethyl-1,3,2-dioxaborinan-2-yl)phenyl]acetonitrile；2-[4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenyl]acetonitrile
• 化学式: C₁₃H₁₆BNO₂
• 分子量: 229.087
• InChiKey: ABRQBFUTHRPJKV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.52
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  42.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenyl)acetonitrile 、 methyl 4-(methanesulfonyloxy)benzoate 在 bis(1,5-cyclooctadiene)nickel (0) 、 potassium phosphate 、 三环己基膦 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以77%的产率得到methyl 4'-(cyanomethyl)-[1,1'-biphenyl]-4-carboxylate
  参考文献：
  名称：

  Ni(COD)₂/PCy₃ Catalyzed Cross-Coupling of Aryl and Heteroaryl Neopentylglycolboronates with Aryl and Heteroaryl Mesylates and Sulfamates in THF at Room Temperature

  摘要：

  Reaction conditions for the Ni(COD)(2)/PCy3 catalyzed cross-coupling of aryl neopentylglycolboronates with aryl mesylates were developed. By using optimized reaction conditions, Ni(COD)(2)/PCy3 was shown to be a versatile catalyst for the cross-coupling of a diversity of aryl neopentylglycolboronates with aryl and heteroaryl mesylates and sulfamates containing both electron-donating and electron-withdrawing substituents in their para, ortho, and meta positions in THF at room temperature. This Ni-catalyzed cross-coupling of aryl neopentylglycolboronates is also effective for the synthesis of heterobiaryls and biaryls containing electrophilic functionalities sensitive to organolithium and organomagnesium derivatives. In combination with the recently developed Ni-catalyzed neopentylglycolborylation, all Ni-catalyzed routes to functional biaryls and heterobiaryls are now easily accessible.

  DOI：

  10.1021/jo202037x
• 作为产物：
  描述：

  neopentylglycolborane 、 对氯苯乙腈 在 1,1'-bis(diphenylphosphino)ferrocene 、 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以60%的产率得到2-(4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenyl)acetonitrile
  参考文献：
  名称：

  NiCl 2（dppp）/ dppf混合配体体系催化的氯化芳基的新戊二醇缩丁酸酯化

  摘要：

  发现具有5 mol％dppf的10 mol％NiCl 2（dppp）混合配体体系是一种用于多种戊基电子和弱电子芳基氯的新戊基糖基化的极有效催化剂。优化表明，具有10％dppf的5 mol％催化剂甚至更有效。这些结果凸显了Ni催化中催化剂与大肠菌之间关系的复杂性，以及混合配体组合在催化剂设计中的好处。

  DOI：

  10.1021/ol902155e

文献信息

• Neopentylglycolborylation of Aryl Chlorides Catalyzed by the Mixed Ligand System NiCl₂(dppp)/dppf
  作者：Costel Moldoveanu、Daniela A. Wilson、Christopher J. Wilson、Patrick Corcoran、Brad M. Rosen、Virgil Percec

  DOI：10.1021/ol902155e

  日期：2009.11.5

  The mixed ligand system 10 mol % NiCl2(dppp) with 5 mol % dppf was discovered to be an extremely efficient catalyst for the neopentylglycolborylation of a diversity of electron-rich and electron-deficient aryl chlorides. Optimization showed that 5 mol % catalyst with 10% dppf was even more efficient. These results highlight the complexity of the relationship between catalyst and coligand in Ni catalysis

  发现具有5 mol％dppf的10 mol％NiCl 2（dppp）混合配体体系是一种用于多种戊基电子和弱电子芳基氯的新戊基糖基化的极有效催化剂。优化表明，具有10％dppf的5 mol％催化剂甚至更有效。这些结果凸显了Ni催化中催化剂与大肠菌之间关系的复杂性，以及混合配体组合在催化剂设计中的好处。
• Copper(I)-Catalyzed Carboxylation of Aryl- and Alkenylboronic Esters
  作者：Jun Takaya、Satoshi Tadami、Kazutoshi Ukai、Nobuharu Iwasawa

  DOI：10.1021/ol800829q

  日期：2008.7.3

  The copper(I)-catalyzed carboxylation reaction of aryl- and alkenylboronic esters proceeded smoothly under CO(2) to give the corresponding carboxylic acid in good yield. This reaction showed wide generality with higher functional group tolerance compared to the corresponding Rh(I)-catalyzed reaction.
• Rhodium(I)-Catalyzed Carboxylation of Aryl- and Alkenylboronic Esters with CO₂
  作者：Kazutoshi Ukai、Masao Aoki、Jun Takaya、Nobuharu Iwasawa

  DOI：10.1021/ja061232m

  日期：2006.7.1

  When the esters of arylboronic acids with 2,2-dimethylpropan-1,3-diol were treated with a catalytic amount of [Rh(OH)(cod)]2 in the presence of 1,3-bis(diphenylphosphino)propane and CsF in dioxane at 60 degrees C under carbon dioxide atmosphere, the benzoic acid derivatives were obtained in good yields. Reactions of alkenylboronic esters also proceeded under similar conditions to give alpha,beta-unsaturated carboxylic acids. As these boronic esters are now easily available through coupling or direct borylation reactions, this method would be a useful method for the preparation of various functionalized aryl- and alkenyl-carboxylic acids.
• Ni(COD)₂/PCy₃ Catalyzed Cross-Coupling of Aryl and Heteroaryl Neopentylglycolboronates with Aryl and Heteroaryl Mesylates and Sulfamates in THF at Room Temperature
  作者：Pawaret Leowanawat、Na Zhang、Ana-Maria Resmerita、Brad M. Rosen、Virgil Percec

  DOI：10.1021/jo202037x

  日期：2011.12.16

  Reaction conditions for the Ni(COD)(2)/PCy3 catalyzed cross-coupling of aryl neopentylglycolboronates with aryl mesylates were developed. By using optimized reaction conditions, Ni(COD)(2)/PCy3 was shown to be a versatile catalyst for the cross-coupling of a diversity of aryl neopentylglycolboronates with aryl and heteroaryl mesylates and sulfamates containing both electron-donating and electron-withdrawing substituents in their para, ortho, and meta positions in THF at room temperature. This Ni-catalyzed cross-coupling of aryl neopentylglycolboronates is also effective for the synthesis of heterobiaryls and biaryls containing electrophilic functionalities sensitive to organolithium and organomagnesium derivatives. In combination with the recently developed Ni-catalyzed neopentylglycolborylation, all Ni-catalyzed routes to functional biaryls and heterobiaryls are now easily accessible.
• Zero-Valent Metals Accelerate the Neopentylglycolborylation of Aryl Halides Catalyzed by NiCl₂-Based Mixed-Ligand Systems
  作者：Pawaret Leowanawat、Ana-Maria Resmerita、Costel Moldoveanu、Chi Liu、Na Zhang、Daniela A. Wilson、Lisa M. Hoang、Brad M. Rosen、Virgil Percec

  DOI：10.1021/jo101718v

  日期：2010.11.19

  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