4-Methyl-2-oxo-2λ⁵-[1,3,2]dioxaphospholan-2-ol anion | 48100-68-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: 4-Methyl-2-oxo-2λ⁵-[1,3,2]dioxaphospholan-2-ol anion
• 英文别名: 4-methyl-1,3,2-dioxaphospholan-2-olate-2-oxide；4-Methyl-2-oxido-1,3,2lambda5-dioxaphospholane 2-oxide；4-methyl-2-oxido-1,3,2λ5-dioxaphospholane 2-oxide
• CAS: 48100-68-1
• 化学式: C₃H₆O₄P
• 分子量: 137.052
• InChiKey: RYRDKOIZZRUCMC-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  58.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(1,4,7-triazacyclononane)2Co2(OH)3](ClO4)3 、 4-Methyl-2-oxo-2λ⁵-[1,3,2]dioxaphospholan-2-ol anion 以 高氯酸 为溶剂， 生成 [Co₂(OH)2(C₆H₁₅N₃)2(C₃H₆O₄P)]⁽³⁺⁾*3ClO₄^(1-) = [Co₂(OH)2(C₆H₁₅N₃)2(C₃H₆O₄P)](ClO₄)3
  参考文献：
  名称：

  与双核钴 (III) 配合物双配位的磷酸二酯的反应性：反应性取决于离去基团的碱度

  摘要：

  研究了八种磷酸二酯各自与双核 Co(III) 复合物配位的反应性（[Co2(tacn)2(OH)2{O2P(OR)2}]3+；tacn = 1,4,7-三氮杂环壬烷）。其中四个配合物由取代的苯基甲基磷酸酯（取代基 mF，p-NO2 (1a)；p-NO2 (1b)；m-NO2 (1c)；未取代的 (1d)）和两个取代的苯基 2-羟丙基磷酸酯配位(取代基p-NO 2 (2a)；未取代的(2b))。还研究了与双核 Co(III) 配合物（1,2-磷酸丙酯 (3)；磷酸二甲酯 (4)）配位的磷酸二烷基酯的反应性。1a 到 1d 中磷酸二酯的水解是通过分子内氧化物攻击桥接磷酸盐而发生的，而 3 的水解主要通过分子间氢氧化物攻击桥接磷酸盐而发生。2a 中的二酯通过分子内氧化物攻击裂解，而 2b 中的二酯通过分子内酯交换裂解。磷酸二甲酯从 4 解离出来，没有任何可观察到的二酯裂解。天...

  DOI：

  10.1021/ja980660s
• 作为产物：
  描述：

  在 sodium hydroxide 、 HEPES buffer 作用下， 生成 4-Methyl-2-oxo-2λ⁵-[1,3,2]dioxaphospholan-2-ol anion
  参考文献：
  名称：

  Polyethylene Imine Derivatives (‘Synzymes') Accelerate Phosphate Transfer in the Absence of Metal

  摘要：

  The efficient integration of binding, catalysis, and multiple turnovers remains a challenge in building enzyme models. We report that systematic derivatization of polyethylene imine (PEI) with alkyl (C2-C12), benzyl, and guanidinium groups gives rise to catalysts ('synzymes') with rate accelerations (k(cat)/k(uncat)) of up to 10(4) for the intramolecular transesterification of 2-hydroxypropyl-p-nitrophenyl phosphate, HPNP, in the absence of metal. The synzymes exhibit saturation kinetics (K-M approximate to 250 mu M, k(cat) approximate to 0.5 min(-1)) and up to 2340 turnovers per polymer molecule. Catalysis can be specifically and competitively inhibited by anionic and hydrophobic small molecules. The efficacy of catalysis is determined by the PEI derivatization pattern. The derivatization reagents exert a synergistic effect, i.e., their combinations increase catalysis by more than the sum of each single modification. The pH-rate profile for k(cat)/K-M is bell shaped with a maximum at pH 7.85 and can be explained as a combination of two effects that both have to be operative for optimal activity: K-M increases at high pH due to deprotonation of PEI amines that bind the anionic substrate and k(cat) decreases as the availability of hydroxide decreases at low pH. Thus, catalysis is based on substrate binding by positively charged amine groups and the presence of hydroxide ion in active sites in an environment that is tuned for efficient catalysis. Inhibition studies suggest that the basis of catalysis and multiple turnovers is differential molecular recognition of the doubly negatively charged transition state (over singly charged ground state and product): this contributes a factor of at least 5-10-fold to catalysis and product release.

  DOI：

  10.1021/ja069095g

文献信息

• Factors Influencing the Activity of Nanozymes in the Cleavage of an RNA Model Substrate
  作者：Czescik、Zamolo、Darbre、Mancin、Scrimin

  DOI：10.3390/molecules24152814

  日期：——

  A series of 2-nm gold nanoparticles passivated with different thiols all featuring at least one triazacyclonanone-Zn(II) complex and different flanking units (a second Zn(II) complex, a triethyleneoxymethyl derivative or a guanidinium of arginine of a peptide) were prepared and studied for their efficiency in the cleavage of the RNA-model substrate 2-hydroxypropyl-p-nitrophenyl phosphate. The source of catalysis for each of them was elucidated from the kinetic analysis (Michaelis–Menten profiles, pH dependence and kinetic isotope effect). The data indicated that two different mechanisms were operative: One involving two Zn(II) complexes and the other one involving a single Zn(II) complex and a flanking guanidinium cation. The mechanism based on a dinuclear catalytic site appeared more efficient than the one based on the cooperativity between a metal complex and a guanidinium.

  一系列经不同硫醇保护的2纳米金纳米颗粒被制备并研究其在裂解RNA模型底物2-羟基丙基对硝基苯磷酸酯中的效率。通过动力学分析（迈克尔斯-门特恩曲线、pH依赖性和动力学同位素效应）阐明了它们各自的催化来源。数据表明存在两种不同的作用机制：一种涉及两个锌（II）络合物，另一种涉及单个锌（II）络合物和一个侧链胍基阳离子。基于双核催化位点的机制似乎比基于金属络合物和胍基之间的协同作用更有效。
• Synthesis of RNAse active site model systems using a steroid template
  作者：Thorsten Oost、Markus Kalesse

  DOI：10.1016/s0040-4020(97)00526-7

  日期：1997.6

  which guanidinium and imidazole moieties, necessary for the transesterification/cleavage, are assembled. By changing the stereochemistry at C11 of 2, and varying the guanidinium side chains, active compounds 9, 11, 13, 15 with different hydrolytic behavior are obtained. Comparison of the steroid compounds clearly demonstrates that changes in the geometry can influence the cleavage reaction of RNA analogs

  描述了RNA酶活性位点模型系统。刚性甾体骨架用作模板，在该模板上组装了酯基转移/裂解所需的胍和咪唑部分。通过在C11改变立体化学2，并改变胍侧链，活性化合物9，11，13，15具有不同的水解行为获得。类固醇化合物的比较清楚地表明，几何形状的变化会影响RNA类似物的裂解反应。此外，分子内碱基可以提高切割速率。活性最高的双（胍）化合物9的pK a值 已经确定并且已经讨论了裂解反应的pH依赖性。
• Copper(II) and Zinc(II) Complexes of Conformationally Constrained Polyazamacrocycles as Efficient Catalysts for RNA Model Substrate Cleavage in Aqueous Solution at Physiological pH
  作者：Daniel Bím、Eva Svobodová、Václav Eigner、Lubomír Rulíšek、Jana Hodačová

  DOI：10.1002/chem.201601175

  日期：2016.7.18

  As part of a quest for efficient artificial catalysts of RNA phosphodiester bond cleavage, conformationally constrained mono‐ and bis‐polyazamacrocycles in which tri‐ or tetraazaalkane chains link the ortho positions of a benzene ring were synthesized. The catalytic activities of mono‐ and dinuclear copper(II) and zinc(II) complexes of these polyazamacrocycles towards cleavage of the P−O bond in 2

  为了寻求有效的RNA磷酸二酯键裂解人工催化剂的一部分，构象受限的单或双聚氮杂大环，其中三氮杂或四氮杂烷烃链连接邻位合成苯环的位置。确定了这些聚氮杂大环的单核和双核铜（II）和锌（II）配合物对pH为7的水溶液中2-羟丙基-4-硝基苯基磷酸酯（HPNP）中P-O键的裂解的催化活性。仅在大环中掺入三个氮原子的配体配合物被证明能够有效催化HPNP酯交换反应。的双核配合物被发现是大约两倍的效率是它们的单核对应，并与计算出的速率常数显示出米氏饱和动力学ķ猫≈10 -4 小号-1。通过量子化学计算（DFT / COSMO-RS），描述了一些合理的反应坐标。通过将计算出的势垒与实验动力学数据相关联，揭示了两种可能的反应情况，活化自由能为20–25 kcal mol -1。
• Rapid Three-Step Cleavage of RNA and DNA Model Systems Promoted by a Dinuclear Cu(II) Complex in Methanol. Energetic Origins of the Catalytic Efficacy
  作者：Zhong-Lin Lu、C. Tony Liu、Alexei A. Neverov、R. Stan Brown

  DOI：10.1021/ja073780l

  日期：2007.9.1

  kinetics with a k(cat)/K(M) value of 30 M(-1) s(-1) which is 3.8 x 10(7)-fold greater than the methoxide promoted reaction of 3 (7.9 x 10(-7) M(-1) s(-1)). A free energy calculation indicates that the binding of 2-Cu(II)(2):(-OCH(3)) to the transition states for 1 and 3 cleavage stabilizes them by -21 and -24 kcal/mol, respectively, relative to that of the methoxide promoted reactions. The results are compared

  1,3-双-N(1)-(1,5,9-三氮杂环十二烷基)丙烷与相关甲醇盐 (2-Cu(II)(2):(-OCH(3) )) 制备，及其与 RNA 模型（2-羟丙基-对硝基苯基磷酸酯 (1, HPNPP)）和两个 DNA 模型（甲基对硝基苯基磷酸酯 (3) 和异丁基对氯苯基磷酸酯）的反应动力学(4)) 在 (s)(s) pH 7.2 +/- 0.2 的甲醇溶液中进行研究。2-Cu(II)(2):(-OH)(H(2)O)(CF(3)SO(3)-)(3):0.5CH(3)CH(2)的X射线衍射结构)OCH(2)CH(3) 和 2-Cu(II)(2):(-OH)((C(6)H(5)CH(2)O)(2)PO(2)-)( CF(3)SO(3)-)2 显示了第一个复合物中两个 Cu(II) 离子之间桥连 -OH 和 H(2)O 的配位模式，以及第二个复合物中桥连 -OH 和磷酸盐基团之间的配位模式。对 1
• Structure, Equilibrium and Ribonuclease Activity of Copper(II) and Zinc(II) Complexes Formed with a Dinucleating Bis-Imidazole Ligand
  作者：Tamás Gajda、Roland Krämer、Attila Jancsó

  DOI：10.1002/1099-0682(200007)2000:7<1635::aid-ejic1635>3.0.co;2-j

  日期：2000.7

  and M2L−2H species are present in solution in the neutral pH range, having analogous structures as described above for the crystalline complexes. The zinc(II)-bimido (2/1) system, in a 65% EtOH-H2O mixed solvent, shows an important increase of hydrolytic activity, parallel with the formation of the Zn2L−2H species, with a sigmoidal pH-rate profile modelling both steps of RNA hydrolysis. The kcat value

  报道了一种新的潜在双核双咪唑配体 N,N'-双 (5-甲基咪唑-4-基甲基)-的铜 (II) 和锌 (II) 复合物的合成、晶体结构、溶液平衡和核糖核酸酶活性1,3-二氨基丙-2-醇（bimido）。[Zn(bimido)Cl]NO3 中的锌 (II) 离子在略微扭曲的四方锥体环境中配位，bimido 的四个 N 原子位于基础位置，Cl− 离子位于轴向位置。[Cu2(bimido−1H)(DPP)(ClO4)(CH3OH)]ClO4·1/2 H2O（DPP = 磷酸二苯酯）中的两个铜 (II) 离子通过双亚氨基的去质子化烷氧基和磷酸盐桥接DPP 组处于 1,3-桥接模式。根据 [M]/[L] 比率，ML 和 M2L-2H 物质存在于中性 pH 范围的溶液中，具有与上述结晶复合物类似的结构。在 65% EtOH-H2O 混合溶剂中，锌 (II)-bimido (2/1) 系统显示出水解活性的显着增加，同时形成