2-[(4-methylphenyl)sulfonyl]-2,3,1-benzodiazaborinin-1(2H)-ol | 22959-81-5

• 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: 2-[(4-methylphenyl)sulfonyl]-2,3,1-benzodiazaborinin-1(2H)-ol
• 英文别名: Diazaborine；1-hydroxy-2-(4-methylphenyl)sulfonyl-2,3,1-benzodiazaborinine
• CAS: 22959-81-5
• 化学式: C₁₄H₁₃BN₂O₃S
• 分子量: 300.146
• InChiKey: UQIDNSKBUXCODH-UHFFFAOYSA-N

物化性质

• 熔点：
  156-159°C
• 沸点：
  504.7±43.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)
• 溶解度：
  氯仿（微溶）、甲醇（微溶、加热）

计算性质

• 辛醇/水分配系数(LogP)：
  0.72
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  78.4
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-[(4-methylphenyl)sulfonyl]-2,3,1-benzodiazaborinin-1(2H)-ol 以 甲醇 为溶剂， 生成 1-methoxy-1H-2,3,1,-benzoxazaborine
  参考文献：
  名称：

  Planar Boron Heterocycles with Nucleic Acid-Like Hydrogen-Bonding Motifs

  摘要：

  To promote the development of boron-containing purine analogues that exist in planar, non-zwitterionic dominant structural form in aqueous solution, rigorous solution and solid state structural analyses of 1-hydroxy-1H-2,3,1-benzoxazaborine (1), 1,2-dihydro-1-hydroxy-2,3,1-benzodiazaborine (2), and related 2,3,1-benzodiheteraborines were undertaken. With the aid of isotope-enriched compounds, a multisolvent H-1, C-13, B-11, and N-15 NMR spectroscopic analysis of 1 and 2 was conducted, providing structurally-diagnostic chemical shift data for all non-oxygen atoms that constitute their heterocyclic peripheries. In addition, single-crystal X-ray diffraction analyses of 1 and 2 were performed. In stark contrast to their 2,4,1 isomeric counterparts, the 2,3,1-benzoxaza- and benzodiazaborines exist in planar structural form in protic solution and in the solid state and display proton dissociative and associative tendencies reflective of the predominant Bronsted, yet still Lewis acidic-capable character of the B-OH group together with the basic one at the C4-N3 imine group. In the solid state, 1 and 2 display intermolecular hydrogen-bonding patterns not too dissimilar from the motifs of certain natural nucleic acid bases. Diazaborine 2 was shown by VT-NMR to undergo a triple hydrogen-bonding solution association with a 2',3',5'-tri-O-protected cytidine in a demonstration of one biomimetic potential held by a 1-hydroxy-2,3,1-diheteraborine periphery. In general, 1, 2, and related 1-hydroxy-2,3,1-benzodiheteraborine heterocycles were found to be characterized by an environment-dependent O1-->N3 Bronsted prototropy and B-OH group Bronsted/Lewis acid ambidency so sensitive and subtle that certain past difficulties encountered in attempts to delineate their physicochemical properties now become readily appreciated.

  DOI：

  10.1021/ja963784i
• 作为产物：
  描述：

  benzaldehyde p-toluenesulfonylhydrazone 在 三溴化硼 作用下， 以 四氯化碳 为溶剂， 生成 2-[(4-methylphenyl)sulfonyl]-2,3,1-benzodiazaborinin-1(2H)-ol
  参考文献：
  名称：

  2,3,1-Diazaborines的新合成

  摘要：

  描述了一种制备2,3,1-二氮杂硼烷的新方法。建议通过离析物的磺酰基基团促进和邻位观察到的通过卤化硼的亲电攻击形成的C，B键。

  DOI：

  10.1002/hlca.19780610128

文献信息

• Diazaborines Are a Versatile Platform to Develop ROS‐Responsive Antibody Drug Conjugates**
  作者：João P. M. António、Joana Inês Carvalho、Ana S. André、Joana N. R. Dias、Sandra I. Aguiar、Hélio Faustino、Ricardo M. R. M. Lopes、Luis F. Veiros、Gonçalo J. L. Bernardes、Frederico A. Silva、Pedro M. P. Gois

  DOI：10.1002/anie.202109835

  日期：2021.12

  The oxidation of physiologically stable diazaborines in the presence of reactive oxygen species (ROS) is the key to the construction of ROS-responsive antibody–drug conjugates. These conjugates are a new class of therapeutics that combine the lethality of potent cytotoxic drugs with the targeting ability of antibodies to selectively deliver drugs to cancer cells.

  在活性氧 (ROS) 存在下，生理稳定的二氮杂硼化物的氧化是构建 ROS 响应性抗体-药物偶联物的关键。这些偶联物是一类新的治疗方法，它将强效细胞毒性药物的杀伤力与抗体的靶向能力相结合，选择性地将药物输送到癌细胞。
• Synthesis, Characterization, and Antibacterial Activity of Structurally Complex 2-Acylated 2,3,1-Benzodiazaborines and Related Compounds
  作者：Divya Kanichar、Lance Roppiyakuda、Ewa Kosmowska、Michelle A. Faust、Kim P. Tran、Felicia Chow、Elena Buglo、Michael P. Groziak、Evan A. Sarina、Marilyn M. Olmstead、Isba Silva、H. Howard Xu

  DOI：10.1002/cbdv.201400007

  日期：2014.9

  the anhydro dimers, 17c, revealed it to have an unprecedented structure featuring a double intramolecular O→B chelation. The crystal structure of another compound, 37, showed it to be based on a new pentacyclic B heterocycle framework. Nine compounds were found to possess activities against E. coli, and two others were active against M. smegmatis. The finding that these two contain isoniazid covalently

  合成，表征和测试了一组2-酰化的2,3,1-苯并二氮杂硼烷和一些相关的硼杂环对大肠杆菌和耻垢分枝杆菌的抗菌活性。通过高场溶液NMR，发现迄今未知的2-酰基-1-羟基-2,3,1-二氮杂硼烷类化合物能够沿着由开放a组成的连续体以几种可相互转化的结构形式存在。单体B-羟基重氮茶碱b和脱水二聚体c。脱水二聚体之一17c的X射线晶体学分析表明，它具有前所未有的结构，具有双重分子内O→B螯合的特征。另一个化合物37的晶体结构表明，它基于新的五环B杂环骨架。发现9种化合物对大肠杆菌具有活性，其他两个人则活跃于耻垢分枝杆菌。这两个在其结构中包含共价嵌入的异烟肼的发现表明，它们可能在体内充当了这种众所周知的抗结核药的前药。
• Lewis or Brønsted? A Rectification of the Acidic and Aromatic Nature of Boranol-Containing Naphthoid Heterocycles
  作者：M. Zain H. Kazmi、Jason P. G. Rygus、Hwee Ting Ang、Marco Paladino、Matthew A. Johnson、Michael J. Ferguson、Dennis G. Hall

  DOI：10.1021/jacs.1c02462

  日期：2021.7.14

  hemiboronic acids may possess sufficient aromatic character to act as Brønsted acids and form a boron oxy conjugate base, thereby avoiding the disruption of ring aromaticity that would occur with a tetravalent boronate anion. Until now no firm evidence existed to ascertain the structure of the conjugate base and the aromatic character of the boron-containing ring of hemiboronic “naphthoid” isosteres. Here

  含硼杂环在从药物发现到材料科学的各种应用中都很重要；因此，为了优化这些功能，需要清楚地了解它们的结构和反应性。尽管硼酸的硼醇 (B-OH) 单元表现为路易斯酸以形成四价三羟基硼酸盐共轭碱，但有人提出假芳族半硼酸可能具有足够的芳香性以充当布朗斯台德酸并形成硼氧共轭碱，从而避免了四价硼酸阴离子会发生的环芳香性的破坏。到目前为止，还没有确凿的证据来确定共轭碱的结构和半硼“萘酚”等排体的含硼环的芳香特性。这里，这些问题通过对一系列模型苯并二氮杂硼和苯并二氮杂硼萘烷类化合物的实验、光谱、X 射线晶体学和计算研究相结合来解决。尽管这些半硼杂环明确显示在水溶液中表现为路易斯酸，但硼氮杂环衍生物具有部分芳香性，前提是它们的氮孤电子对足以参与扩展的离域化。正如动态交换和交叉实验所证明的那样，这些杂环在中性水性介质中是稳定的，并且它们的测量 p 尽管这些半硼杂环明确显示在水溶液中表现为路易斯酸，但硼氮杂环衍生
• Diazaborines oxidize slowly with H₂O₂ but rapidly with peroxynitrite in aqueous buffer
  作者：Jack G. Haggett、Gun Su Han、Angela R. Moser、Julian V. A. Golzwarden、Shubham Vyas、Dylan W. Domaille

  DOI：10.1039/d1ob01668g

  日期：——

  Reactive oxygen species (ROS) such as hydrogen peroxide (H2O2) and peroxynitrite (ONOO−) oxidize arylboronic acids to their corresponding phenols. When used in molecular imaging probes and in ROS-responsive molecules, however, simple arylboronic acids struggle to discriminate between H2O2 and ONOO− because of their fast rate of reaction with both ROS. Here, we show that diazaborines (DABs) react slowly

  过氧化氢 (H 2 O 2 ) 和过氧亚硝酸盐 (ONOO - )等活性氧 (ROS) 可将芳基硼酸氧化为相应的酚类。然而，当用于分子成像探针和 ROS 响应分子时，简单的芳基硼酸很难区分 H 2 O 2和 ONOO -因为它们与两种 ROS 反应速度快。在这里，我们显示二氮杂硼烷 (DAB) 与 H 2 O 2反应缓慢，但在水性缓冲液中与过氧亚硝酸盐反应迅速。除了它们与 H 2 O 2的缓慢反应外，DAB 与 H 2氧化的直接产物O 2和ONOO -可以产生动力学捕获的C N Z -异构体，其与其E -异构体缓慢平衡。总之，我们的工作表明，与芳基硼酸相比，二氮硼烷在 H 2 O 2和 ONOO之间表现出更强的动力学区分，为化学生物学中基于二氮硼烷的工具开辟了新的机会。
• Sulfonyl Diazaborine ‘Click’ Chemistry Enables Rapid and Efficient Bioorthogonal Labeling**
  作者：Arnab Chowdhury、Saurav Chatterjee、Apoorv Kushwaha、Sidhanta Nanda、T. J. Dhilip Kumar、Anupam Bandyopadhyay

  DOI：10.1002/chem.202300393

  日期：2023.7.20

  Here we have systematically developed and deliberated an efficient bioorthogonal reaction via the rapid formation of sulfonyl-diazaborine. The conjugation is robust to demonstrate suitable application in cancer cell imaging and treatment.

  在这里，我们系统地开发和研究了一种通过快速形成磺酰基二氮杂硼啉的有效生物正交反应。该结合是稳健的，证明其在癌细胞成像和治疗中的合适应用。