(3,5-diethylphenyl)boronic acid | 1147894-88-9

• 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: (3,5-diethylphenyl)boronic acid
• 英文别名: (3,5-Diethylphenyl)boronicacid
• CAS: 1147894-88-9
• 化学式: C₁₀H₁₅BO₂
• 分子量: 178.039
• InChiKey: MKLPRIKMGJFQPF-UHFFFAOYSA-N

物化性质

• 沸点：
  330.8±52.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.49
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3,5-diethylphenyl)boronic acid 在 对甲苯磺酸 、 三苯基膦 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 甲醇 、 甲苯 、 苯 为溶剂， 反应 38.67h， 生成 {3,5-diiodo-N-[2,6-bis(3,5-diethylphenyl)phenyl]salicylaldiminato-κ²-N,O}methylpyridine nickel(II)
  参考文献：
  名称：

  Monofunctional Hyperbranched Ethylene Oligomers

  摘要：

  The neutral kappa N-2,O-salicylaldiminato Ni(II) complexes [kappa N-2,O-{(2,6-(3',5'-R2C6H3)(2)C6H3-N=C(H)-(3,5-I-2-2-O-C6H2)}]NiCH3(pyridine)] (1a-pyr, R = Me; 1b-pyr, R = Et; 1c-pyr, R = iPr) convert ethylene to hyperbranched low-molecular-weight oligomers (M-n ca. 1000 g mol(-1)) with high productivities. While all three catalysts are capable of generating hyperbranched structures, branching densities decrease significantly with the nature of the remote substituent along Me > Et > iPr and oligomer molecular weights increase. Consequently, only 1a-pyr forms hyperbranched structures over a wide range of reaction conditions (ethylene pressure 5-30 atm and 20-70 degrees C). An in situ catalyst system achieves similar activities and identical highly branched oligomer microstructures, eliminating the bottleneck given by the preparation and isolation of Ni Me catalyst precursor species. Selective introduction of one primary carboxylic acid ester functional group per highly branched oligoethylene molecule was achieved by isomerizing ethoxycarbonylation and alternatively cross metathesis with ethyl acrylate followed by hydrogenation. The latter approach results in complete functionalization and no essential loss of branched oligomer material and molecular weight, as the reacting double bonds are close to a chain end. Reduction yielded a monoalcohol-functionalized oligomer. Introduction of one reactive epoxide group per branched oligomer occurs completely and selectively under mild conditions. All reaction steps involved in oligomerization and monofunctionalization are efficient and readily scalable.

  DOI：

  10.1021/ja411945n
• 作为产物：
  描述：

  1-溴-3,5-二乙基苯 在 正丁基锂 、 硫酸 作用下， 以 四氢呋喃 、 正己烷 、 水 为溶剂， 反应 2.5h， 以70%的产率得到(3,5-diethylphenyl)boronic acid
  参考文献：
  名称：

  Monofunctional Hyperbranched Ethylene Oligomers

  摘要：

  The neutral kappa N-2,O-salicylaldiminato Ni(II) complexes [kappa N-2,O-{(2,6-(3',5'-R2C6H3)(2)C6H3-N=C(H)-(3,5-I-2-2-O-C6H2)}]NiCH3(pyridine)] (1a-pyr, R = Me; 1b-pyr, R = Et; 1c-pyr, R = iPr) convert ethylene to hyperbranched low-molecular-weight oligomers (M-n ca. 1000 g mol(-1)) with high productivities. While all three catalysts are capable of generating hyperbranched structures, branching densities decrease significantly with the nature of the remote substituent along Me > Et > iPr and oligomer molecular weights increase. Consequently, only 1a-pyr forms hyperbranched structures over a wide range of reaction conditions (ethylene pressure 5-30 atm and 20-70 degrees C). An in situ catalyst system achieves similar activities and identical highly branched oligomer microstructures, eliminating the bottleneck given by the preparation and isolation of Ni Me catalyst precursor species. Selective introduction of one primary carboxylic acid ester functional group per highly branched oligoethylene molecule was achieved by isomerizing ethoxycarbonylation and alternatively cross metathesis with ethyl acrylate followed by hydrogenation. The latter approach results in complete functionalization and no essential loss of branched oligomer material and molecular weight, as the reacting double bonds are close to a chain end. Reduction yielded a monoalcohol-functionalized oligomer. Introduction of one reactive epoxide group per branched oligomer occurs completely and selectively under mild conditions. All reaction steps involved in oligomerization and monofunctionalization are efficient and readily scalable.

  DOI：

  10.1021/ja411945n

文献信息

• Synthesis of substituted (N,C) and (N,C,C) Au(<scp>iii</scp>) complexes: the influence of sterics and electronics on cyclometalation reactions
  作者：Knut T. Hylland、Inga L. Schmidtke、David S. Wragg、Ainara Nova、Mats Tilset

  DOI：10.1039/d2dt00371f

  日期：——

  cyclometalation at Au(III) to take place via an electrophilic aromatic substitution-type mechanism. The formation of Au(III) pincer complexes from tridentate (N,C,C) ligands was investigated by synthesis and DFT calculations, in order to assess the feasibility of C(sp3)–H bond activation as a synthetic pathway to (N,C,C) cyclometalated Au(III) complexes. It was found that C(sp3)–H bond activation is feasible for

  环金属化 Au( III ) 配合物因其催化、药用和光物理特性而备受关注。在此，我们描述了通过环金属化途径合成 (N,C)Au(OAc F ) 2 (OAc F = 三氟乙酸酯) 和 (N,C,C)AuOAc F类型的衍生物，其中 (N,C) 和(N,C,C) 是螯合 2-芳基吡啶配体。通过在一个或两个环上用电子供体或受体取代基取代 2-芳基吡啶核来探索合成的范围。值得注意的是，从相应的配体和 Au(OAc) 3中一步即可获得多种功能化的 Au( III ) 配合物，消除了对有机汞中间体的需求，这通常用于类似的合成。使用 DFT 计算、 15 N NMR 光谱和单晶 X 射线衍射分析评估配体骨架中的取代基对所得配合物的影响。结合自然电荷分析的实验研究发现，(N,C) 配体的电子特性与其进行环金属化的能力之间存在相关性，表明 Au( III ) 处的环金属化是通过亲电子芳香取代型机制发生的.
• Regio‐ and Enantioselective Intermolecular Aminofluorination of Alkenes via Iodine(I)/Iodine(III) Catalysis**
  作者：Michael Schäfer、Timo Stünkel、Constantin G. Daniliuc、Ryan Gilmour

  DOI：10.1002/anie.202205508

  日期：2022.8.8

  The regio- and enantioselective, intermolecular vicinal fluoroamination of α-trifluoromethyl styrenes was achieved by enantioselective II/IIII catalysis. The transient iodonium intermediate is intercepted with nitriles, which function as both the solvent and nucleophile. In situ Ritter reaction provides direct access to the corresponding amides (up to 89 % yield). Crystallographic analyses of the β-fluoroamide

  α-三氟甲基苯乙烯的区域和对映选择性、分子间邻位氟胺化是通过对映选择性 I/I III催化实现的。短暂的碘鎓中间体被腈拦截，腈既充当溶剂又充当亲核试剂。原位 Ritter 反应可直接获得相应的酰胺（产率高达 89%）。 β-氟酰胺产品的晶体学分析显示出高度预组织的构象，表现出立体电子的疏忽效应。
• C–H Bonds as Functional Groups: Simultaneous Generation of Multiple Stereocenters by Enantioselective Hydroxylation at Unactivated Tertiary C–H Bonds
  作者：Andrea Palone、Guillem Casadevall、Sergi Ruiz-Barragan、Arnau Call、Sílvia Osuna、Massimo Bietti、Miquel Costas

  DOI：10.1021/jacs.2c10148

  日期：2023.7.26

  Enantioselective C–H oxidation is a standing chemical challenge foreseen as a powerful tool to transform readily available organic molecules into precious oxygenated building blocks. Here, we describe a catalytic enantioselective hydroxylation of tertiary C–H bonds in cyclohexane scaffolds with H2O2, an evolved manganese catalyst that provides structural complementary to the substrate similarly to

  对映选择性 C-H 氧化是一项长期的化学挑战，预计它将成为将容易获得的有机分子转化为珍贵的含氧结构单元的强大工具。在这里，我们描述了环己烷支架中叔 C-H 键与 H 2 O 2的催化对映选择性羟基化，H 2 O 2 是一种进化的锰催化剂，可提供与底物的结构互补，类似于酶活性位点中操作的锁和钥匙识别。理论计算揭示了对映选择性是通过互补的弱非共价相互作用网络将底物支架精确地安装到催化位点来控制的。立体保留 C( sp 3 )–H 羟基化可一步生成多个立体中心（最多 4 个），可通过传统方法正交操作，提供从单一前体到各种手性支架的快速访问。
• Iron-Catalyzed Asymmetric Epoxidation of β,β-Disubstituted Enones
  作者：Yasuhiro Nishikawa、Hisashi Yamamoto

  DOI：10.1021/ja201873d

  日期：2011.6.8

  The combination of Fe(OTf2) and novel phenanthroline ligands enables the catalytic asymmetric epwddation of acyclic beta,beta-disubstituted enones, which have been a heretofore inaccessible substrate class. The reaction provides highly enantioenriched alpha,beta-epoxyketones (up to 92% ee) that can be further converted to functionalized beta-ketoaldehydes with an all-carbon quaternary center.
• Asymmetric Homoenolate Additions to Acyl Phosphonates through Rational Design of a Tailored <i>N</i>-Heterocyclic Carbene Catalyst
  作者：Ki Po Jang、Gerri E. Hutson、Ryne C. Johnston、Elizabeth O. McCusker、Paul H.-Y. Cheong、Karl A. Scheidt

  DOI：10.1021/ja410932t

  日期：2014.1.8

  A highly selective NHC-catalyzed synthesis of gamma-butyrolactones from the fusion of enals and alpha-ketophosphonates has been developed. Computational modeling of competing transition states guided a rational design strategy to achieve enhanced levels of enantioselectivity with a new tailored C-1-symmetric biaryl-saturated imidazolium-derived NHC catalyst.