isopropyl 2-iodoxybenzoate | 185566-83-0

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: isopropyl 2-iodoxybenzoate
• 英文别名: 1-Oxo-1-propan-2-yloxy-1lambda5,2-benziodoxol-3-one；1-oxo-1-propan-2-yloxy-1λ5,2-benziodoxol-3-one
• CAS: 185566-83-0
• 化学式: C₁₀H₁₁IO₄
• 分子量: 322.099
• InChiKey: QHLKNSYAKZFKGD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  isopropyl 2-iodoxybenzoate 在 水 作用下， 以 氘代二甲亚砜 为溶剂， 生成 异丙醇 、 2-碘酰基苯甲酸
  参考文献：
  名称：

  Hypervalent Iodine Oxidants:  Structure and Kinetics of the Reactive Intermediates in the Oxidation of Alcohols and 1,2-Diols by o-Iodoxybenzoic Acid (IBX) and Dess−Martin Periodinane. A Comparative ¹H-NMR Study

  摘要：

  Alcohols and 1,2-diols oxidation by o-iodoxybenzoic acid (IBX) has been examined by H-1-NMR spectroscopy. Reversible formation of reactive intermediates, iodic esters 5, has been observed, and their structures in DMSO-d(6) solution have been defined as 10-I-4 axial alkoxyiodinane oxides by comparison of the chemical shift difference data with those obtained for Dess-Martin periodinane (DMP)-alcoholate and -diolate adducts. The dichotomous behavior exhibited by IBX and DMP with 1,2-diols can be explained in terms of the different architecture of the reactive intermediates involved in the oxidation. With aliphatic alcohols, kinetic evidences support a two-step reaction mechanism involving a fast pre-equilibrium step leading to 5, followed by a rate-determining disproportionation step. With electronically activated benzyl alcohol, the attainment of preequilibrium is largely dependent on initial water concentration as a consequence of a particularly high k(2) value. The influence of the alcohol structure on measured equilibrium (K-eq) and rate constants (k(2)) and the effect of water on the overall reaction rate are discussed.

  DOI：

  10.1021/jo961044m
• 作为产物：
  描述：

  异丙醇 、 2-碘酰基苯甲酸 以 氘代二甲亚砜 为溶剂， 生成 isopropyl 2-iodoxybenzoate
  参考文献：
  名称：

  Hypervalent Iodine Oxidants:  Structure and Kinetics of the Reactive Intermediates in the Oxidation of Alcohols and 1,2-Diols by o-Iodoxybenzoic Acid (IBX) and Dess−Martin Periodinane. A Comparative ¹H-NMR Study

  摘要：

  Alcohols and 1,2-diols oxidation by o-iodoxybenzoic acid (IBX) has been examined by H-1-NMR spectroscopy. Reversible formation of reactive intermediates, iodic esters 5, has been observed, and their structures in DMSO-d(6) solution have been defined as 10-I-4 axial alkoxyiodinane oxides by comparison of the chemical shift difference data with those obtained for Dess-Martin periodinane (DMP)-alcoholate and -diolate adducts. The dichotomous behavior exhibited by IBX and DMP with 1,2-diols can be explained in terms of the different architecture of the reactive intermediates involved in the oxidation. With aliphatic alcohols, kinetic evidences support a two-step reaction mechanism involving a fast pre-equilibrium step leading to 5, followed by a rate-determining disproportionation step. With electronically activated benzyl alcohol, the attainment of preequilibrium is largely dependent on initial water concentration as a consequence of a particularly high k(2) value. The influence of the alcohol structure on measured equilibrium (K-eq) and rate constants (k(2)) and the effect of water on the overall reaction rate are discussed.

  DOI：

  10.1021/jo961044m
• 作为试剂：
  描述：

  三苯基甲烷 在 C₂₂H₂₂FeN₆O⁽²⁺⁾*2ClO₄^(1-) 、 isopropyl 2-iodoxybenzoate 作用下， 生成 三苯基甲醇
  参考文献：
  名称：

  由四个五齿配体支持的非血红素 FeIV═O 配合物：对 H 和 O 原子转移过程的反应性

  摘要：

  四个新的五齿 N5-供体配体，[ N -(1-甲基-2-咪唑基)甲基- N -(2-吡啶基)-甲基- N -(双-2-吡啶基甲基)-胺] ( L 1 ), [ N-双(1-甲基-2-咪唑基)甲基-N- (双-2-吡啶基甲基)胺] ( L 2 ), ( N- (异喹啉-3-基甲基)-1,1-二(吡啶-2) -基) -N- (吡啶-2-基甲基)甲胺( L 3 )和N , N-双(异喹啉-3-基甲基)-1,1-二(吡啶-2-基)甲胺( L 4 ) , 是基于 N4Py 配体框架合成的，其中 N4Py 母体的一个或两个吡啶基臂被 ( N-甲基) 咪唑基或N- (异喹啉-3-基甲基) 部分取代。使用这四个五齿配体，单核配合物 [Fe II (CH 3 CN)( L 1 )] 2+ ( 1a )、[Fe II (CH 3 CN)( L 2 )] 2+ ( 2a )、[Fe II (CH 3 CN)( L

  DOI：

  10.1021/acs.inorgchem.3c02526

文献信息

• Effects of Noncovalent Interactions on High-Spin Fe(IV)–Oxido Complexes
  作者：Victoria F. Oswald、Justin L. Lee、Saborni Biswas、Andrew C. Weitz、Kaustuv Mittra、Ruixi Fan、Jikun Li、Jiyong Zhao、Michael Y. Hu、Esen E. Alp、Emile L. Bominaar、Yisong Guo、Michael T. Green、Michael P. Hendrich、A. S. Borovik

  DOI：10.1021/jacs.0c03085

  日期：2020.7.8

  properties are proposed to be influenced by the unique microenvironments present in protein active sites. Microenvironments are regulated by non-covalent interactions, such as hydrogen bonds (H-bonds) and electrostatic interactions; however, there is little quantitative information about how these interactions affect crucial properties of high valent metal-oxido complexes. To address this knowledge gap

  高价非血红素 FeIV 氧化物质是生物氧化的关键中间体，它们的性质被认为受蛋白质活性位点中存在的独特微环境的影响。微环境受非共价相互作用的调节，例如氢键（H 键）和静电相互作用；然而，关于这些相互作用如何影响高价金属-氧化物络合物的关键性质的定量信息很少。为了解决这一知识差距，我们引入了一系列与自然界中发现的具有相同 S = 2 自旋基态的 FeIV-氧化配合物，然后系统地探讨了非共价相互作用对其电子、结构和振动特性的影响. 提供对这些复合物的访问的关键设计特征是新的三足配体 [poat] 3-，其中含有次膦酰胺基团。[FeIVpoat(O)] 的一个重要结构方面是包含一个能够结合路易斯酸 (LAII) 的辅助位点；我们使用这个独特的功能来进一步调节铁氧化单元周围的静电环境。实验研究证实，H-键和LAIIs可以直接与FeIV-氧化配合物中的氧化配体相互作用，削弱Fe=O键并对电子结构产生影响。我们发现