bis(catecholboryl) oxide | 3602-36-6

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: bis(catecholboryl) oxide
• 英文别名: catecholborane；dicatecholatobisborylether；2,2'-oxydibenzo[d][1,3,2]dioxaborol；2-(1,3,2-benzodioxaborol-2-yloxy)-1,3,2-benzodioxaborole；Bis-<4,5-benzo-1,3,2-dioxaborolyl-(2)>-aether；bis(benzo-1,3,2-dioxoborolanyl)oxide；bis(benzo-1,3,2-dioxaborolanyl)oxid；2-Oxo-bis(1,3,2-benzodioxaborol)；dipyrocatechol borate；bis-(benzo[1,3,2]dioxaborol-2-yl)-oxide；Bis-(benzo[1,3,2]dioxaborol-2-yl)-oxid；catecholboric anhydride；(catB)2O
• CAS: 3602-36-6
• 化学式: C₁₂H₈B₂O₅
• 分子量: 253.815
• InChiKey: WYHNTLLRXOLHIE-UHFFFAOYSA-N

物化性质

• 熔点：
  79 °C
• 沸点：
  160 °C(Press: 0.1 Torr)
• 密度：
  1.35±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.92
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  bis(catecholboryl) oxide 、 四丁基氟化铵 以 氯仿 为溶剂， 生成
  参考文献：
  名称：

  Complementary anion binding by bidentate boron-containing Lewis acids

  摘要：

  Anion binding by the pyroborates (catB)(2)O (1, cat = O2C6H4-1,2) and (S,S-Ph2C2H2O2B)(2)O (2) has been investigated by spectroscopic, structural and titration methods. 1 has been shown to act as a bifunctional Lewis acid, exemplified by the complementary (1:1) binding of bidentate bases such as acetate and dihydrogen phosphate. The former complex has been characterized in the solid state by X-ray diffraction and a binding constant of 1500 +/- 550 M-1 determined in chloroform solution. The reaction of 2 with acetate, by contrast, leads to breakdown of the Lewis acid chelate and to the formation of the homochiral borate anion [(S,S-Ph2C2H2O2)(2)B](-) in good yield (84% based on the chiral component). (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.01.015
• 作为产物：
  描述：

  B-氯-1,2-苯二酚硼烷 在 乙醚 、 水 作用下， 生成 bis(catecholboryl) oxide
  参考文献：
  名称：

  Gerrard et al., Journal of the Chemical Society, 1959, p. 1529,1531, 1533

  摘要：

  DOI：

文献信息

• Hydroboration of aldehydes, ketones and CO₂ under mild conditions mediated by iron(<scp>iii</scp>) salen complexes
  作者：Samantha Lau、Cei B. Provis-Evans、Alexander P. James、Ruth L. Webster

  DOI：10.1039/d1dt02092g

  日期：——

  The hydroboration of aldehydes, ketones and CO2 is demonstrated using a cheap and air stable [Fe(salen)]2-μ-oxo pre-catalyst with pinacolborane (HBpin) as the reductant under mild conditions. This catalyst system chemoselectively hydroborates aldehydes over ketones and ketones over alkenes. In addition, the [Fe(salen)2]-μ-oxo pre-catalyst shows good efficacy at reducing “wet” CO2 with HBpin at room

  在温和条件下，使用廉价且空气稳定的 [Fe(salen)] 2 -μ-氧代预催化剂和频哪醇硼烷 (HBpin) 作为还原剂，证明了醛、酮和 CO 2的硼氢化。该催化剂体系化学选择性地将醛与酮和酮与烯烃化学选择性地氢硼化。此外，[Fe(salen) 2 ]-μ-oxo 预催化剂在室温下用 HBpin还原“湿”CO 2 方面表现出良好的效果。
• Carbene-9-BBN Ring Expansions as a Route to Intramolecular Frustrated Lewis Pairs for CO₂Reduction
  作者：Tongen Wang、Douglas W. Stephan

  DOI：10.1002/chem.201304870

  日期：2014.3.10

  Reactions of phosphine‐derived carbenes with 9‐borabicyclo[3.3.1]nonane (9‐BBN) result in ring‐expansion reactions to generate novel intramolecular frustrated Lewis pairs (FLPs). These FLPs effect the catalytic reduction of CO2 in the presence of boranes to give BOB and methoxy‐borate species.

  膦衍生的卡宾与9-borabicyclo [3.3.1]壬烷（9-BBN）的反应导致环扩环反应，从而生成新的分子内失意的Lewis对（FLP）。这些FLP在硼烷存在下影响CO 2的催化还原，生成BOB和甲氧基硼酸酯。
• Imido–hydrido complexes of Mo(<scp>iv</scp>): catalysis and mechanistic aspects of hydroboration reactions
  作者：Andrey Y. Khalimon、Philip M. Farha、Georgii I. Nikonov

  DOI：10.1039/c5dt02945g

  日期：——

  Imido–hydrido complexes (ArN)Mo(H)(Cl)(PMe3)3 (1) and (ArN)Mo(H)2(PMe3)3 (2) (Ar = 2,6-diisopropylphenyl) catalyse a variety of hydroboration reactions, including the rare examples of addition of HBCat to nitriles to form bis(borylated) amines RCH2N(BCat)2. Stoichiometric reactivity of complexes 1 and 2 with nitriles and HBCat suggest that catalytic reactions proceed via a series of agostic borylamido

  亚氨基-氢化物络合物（ArN）Mo（H）（Cl）（PMe 3）3（1）和（ArN）Mo（H）2（PMe 3）3（2）（Ar = 2,6-二异丙基苯基）催化各种硼氢化反应，包括将HBCat添加到腈中以形成双（硼化）胺RCH 2 N（BCat）2的罕见例子。配合物1和2与腈和HBCat的化学计量反应性表明，催化反应是通过一系列有害的硼酸酰胺基和硼基氨基配合物进行的。对于复杂1，催化作用是通过在Mo–H键上添加腈而开始的，从而生成（ArN）Mo（Cl）（N CHR）（PMe 3）2；而对于复杂的2个化学计量的反应表明初始添加HBCat以形成agostic复杂沫（H）2（PME 3）3（η 3 -NAr-HBcat）（16）。
• Catalyzed hydroboration of nitrostyrenes and 4-vinylaniline: a mild and selective route to aniline derivatives containing boronate esters
  作者：Christopher M. Vogels、Andreas Decken、Stephen A. Westcott

  DOI：10.1016/j.tetlet.2006.01.144

  日期：2006.4

  from competing hydrogenation and hydroboration of the alkene unit along with reduction of the nitro group. Hydroboration of 4-vinylaniline gave regioselective formation of either the branched or the linear organoboronate ester depending upon the catalyst precursors (i.e., RhCl(PPh3)3 or Rh(acac)(dppe) vs [Cp∗IrCl2]2) used to facilitate this reaction. Hydroboration products were converted to air-stable

  儿茶酚硼烷（HBcat； cat = 1,2-O 2 C 6 H 4）与β-硝基苯乙烯和3-硝基苯乙烯的过渡金属催化反应，导致烯烃单元竞争性氢化和氢硼化以及硝基还原而生成的产物。4-乙烯基苯胺的氢硼化反应可根据所用催化剂前体（即RhCl（PPh 3）3或Rh（acac）（dppe）vs [Cp ∗ IrCl 2 ] 2）而形成支链或线性有机硼酸酯的区域选择性形成。促进这一反应。通过添加频哪醇将硼氢化产物转化为空气稳定的伯胺。
• Catalytic properties of nickel bis(phosphinite) pincer complexes in the reduction of CO2 to methanol derivatives
  作者：Sumit Chakraborty、Yogi J. Patel、Jeanette A. Krause、Hairong Guan

  DOI：10.1016/j.poly.2011.04.030

  日期：2012.1

  however, it reacts with 9-borabicyclo[3.3.1]nonane and pinacolborane to generate a methanol derivative and a boryl formate species, respectively. The catalytic reduction of CO 2 with catecholborane is more effectively catalyzed by a more sterically hindered nickel pincer hydride complex with bulky R groups on the phosphorus donor atoms. The nickel pincer hydride complexes are inactive catalysts for

  摘要用间苯二酚ClP（C 5 H 9）在一个罐中制备了一种新的镍双（亚膦酸酯）夹钳络合物[2,6-（R 2 PO）2 C 6 H 3] NiCl（LR NiCl，R =环戊基） ）2，NiCl 2和4-二甲基氨基吡啶。该夹钳化合物与LiAlH 4的反应产生氢化镍配合物，其能够在室温下快速还原CO 2以得到甲酸镍配合物。两种相关的甲酸镍配合物LR NiOCHO（R =环戊基和异丙基）的X射线结构显示了甲酰基相对于配位平面的“面内”构象。甲酸镍配合物LR NiOCHO（R =环戊基，异丙基和叔丁基）与儿茶酚硼烷的化学计量反应表明，庞大的R基团有助于该反应。LR NiOCHO（R =叔丁基）在室温下不与PhSiH 3反应；但是，它会与9-borabicyclo [3.3.1]壬烷和频哪醇硼烷反应，分别生成甲醇衍生物和甲酸硼基酯。邻苯二酚硼烷对CO 2的催化还原作用更有效地由位阻更大的磷供体原子上