pyrophosphoric acid | 42499-21-8

• 分子结构分类: 无机化合物 - 均质非金属化合物 - 非金属氧阴离子化合物
• 英文名称: pyrophosphoric acid
• 英文别名: [hydroxy(oxido)phosphoryl] phosphate
• CAS: 42499-21-8
• 化学式: 4H*O₇P₂
• 分子量: 177.975
• InChiKey: XPPKVPWEQAFLFU-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  -3.4
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  133
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  fac-[Re(CO)₃(H₂O)₃]OTf 、 pyrophosphoric acid 在 盐酸 、 sodium hydroxide 作用下， 以 水 、 重水 为溶剂， 生成 fac-[Re(CO)3(H2O)(pyrophosphate)](1-)
  参考文献：
  名称：

  Reactions of fac-[Re(CO)₃(H₂O)₃]⁺ with Nucleoside Diphosphates and Thiamine Diphosphate in Aqueous Solution Investigated by Multinuclear NMR Spectroscopy

  摘要：

  Products formed between monoester diphosphates (MDPs) and fac-[Re(CO)(3)(H2O)(3)]OTf at pH 3.6 were examined. Such adducts of the fac [Re(CO)(3)](+) moiety have an uncommon combination of properties for an "inert" metal center in that sharp NMR signals can be observed, yet the products are equilibrating at rates allowing NMR EXSY cross-peaks to be observed. Thiamine diphosphate (TDP) and uridine 5'-diphosphate (5'-UDP) form 1:1 bidentate {P alpha,P beta} chelates, in which the MDP binds Re(l) via P alpha and P beta phosphate groups. Asymmetric centers are created at Re(I) (R-Re/S-Re) and P alpha (Delta/Lambda), leading to four diastereomers. The two mirror pairs of diastereomers (R-Re Delta/S-Re Lambda) and (R-Re Lambda/S-Re Delta) for TDP (no ribose) and for all four diastereorners (R-Re Lambda. R-Re Lambda S-Re Lambda, S-Re Lambda) for 5'-UDP (asymmetric ribose) gave two and four sets of NMR signals for the bound MDP, respectively. P-31 alpha-P-31 alpha EXSY cross-peaks indicate that the fac-[Re(CO)(3)(H2O)({P alpha, P beta} MDP)]- isomers interchange slowly on the NMR time scale, with an average k approximate to 0.8 s-1 at 32 degrees C the EXSY cross-peaks could arise from chirality changes at only Re(l) or at only P alpha. Guanosine 5'-diphosphate (5'.-GDP), with a ribose moiety and a Re(l)-binding base, formed both possible diastereomers (R-Re and S-Re) of the fac-[Re(CO)(3)(H2O)({N7,P beta}GDP)]- macrochelate, with one slightly more abundant diastereomer suggested to be R-Re by Mn2+, ion H-1 NMR signal line-broadening combined with distances from molecular models. Interchange of the diastereomers requires that the coordination site of either N7 or P beta move to the H2O site. P-31 alpha-P-31 alpha EXSY cross-peaks indicate a k approximate to 0.5 s(-1) at 32 degrees C for R-Re-tO-S-Re interchange. The similarity of the rate constants for interchange of fac-[Re(CO)(3)(H2O)({P alpha,P beta}MDP)]- and fac-[Re(CO)(3)(H2O)(tN7,P beta}GD,P)]- adducts suggest strongly that interchange of P beta and H2O coordination positions accounts for the EXSY cross-peaks present in the spectra of all adducts.

  DOI：

  10.1021/ic701038f
• 作为产物：
  描述：

  3-methyl-5-[(1R,4aR,8aR)-5,5,8a-trimethyl-2-methylidenedecahydronaphthalen-1-yl]pent-2-en-1-yl diphosphate 生成 (Z)-biformene 、 pyrophosphoric acid
  参考文献：
  名称：

  摘要：

  DOI：

文献信息

• Enzyme-Catalyzed Intramolecular Enantioselective Hydroalkoxylation
  作者：Shu-Shan Gao、Marc Garcia-Borràs、Joyann S. Barber、Yang Hai、Abing Duan、Neil K. Garg、K. N. Houk、Yi Tang

  DOI：10.1021/jacs.7b01089

  日期：2017.3.15

  method of forming C-O bonds and cyclic ethers in synthetic chemistry. In studying the biosynthesis of the fungal natural product herqueinone, we identified an enzyme that can perform an intramolecular enantioselective hydroalkoxylation reaction. PhnH catalyzes the addition of a phenol to the terminal olefin of a reverse prenyl group to give a dihydrobenzofuran product. The enzyme accelerates the reaction

  氢烷氧基化是合成化学中形成 CO 键和环醚的一种强大而有效的方法。在研究真菌天然产物 Herqueinone 的生物合成过程中，我们确定了一种可以进行分子内对映选择性加氢烷氧基化反应的酶。PhnH 催化苯酚加成到反向异戊二烯基的末端烯烃，得到二氢苯并呋喃产物。与未催化的反应相比，该酶将反应加速了 3 × 105 倍。PhnH 属于具有未知功能域 (DUF3237) 的蛋白质超家族，其中没有成员具有先前已验证的功能。PhnH 的发现表明酶可用于促进对映选择性加氢烷氧基化反应并形成环醚。
• Psoromic Acid is a Selective and Covalent Rab-Prenylation Inhibitor Targeting Autoinhibited RabGGTase
  作者：Céline Deraeve、Zhong Guo、Robin S. Bon、Wulf Blankenfeldt、Raffaella DiLucrezia、Alexander Wolf、Sascha Menninger、E. Anouk Stigter、Stefan Wetzel、Axel Choidas、Kirill Alexandrov、Herbert Waldmann、Roger S. Goody、Yao-Wen Wu

  DOI：10.1021/ja211305j

  日期：2012.5.2

  vesicular transport, is essential for their function. Rab geranylgeranyl transferase (RabGGTase) is responsible for prenylation of Rab proteins. Recently, RabGGTase inhibitors have been proposed to be potential therapeutics for treatment of cancer and osteoporosis. However, the development of RabGGTase selective inhibitors is complicated by its structural and functional similarity to other protein prenyltransferases

  香叶基香叶基异戊二烯与 Rab GTP 酶（细胞内囊泡运输的关键组织者）的翻译后附着对其功能至关重要。Rab 香叶基香叶基转移酶 (RabGGTase) 负责 Rab 蛋白的异戊二烯化。最近，人们提出 RabGGTase 抑制剂是治疗癌症和骨质疏松症的潜在疗法。然而，RabGGTase 选择性抑制剂的开发因其与其他蛋白质异戊二烯基转移酶的结构和功能相似性而变得复杂。在此，我们报告鉴定了天然产物银屑病酸 (PA)，其有效且选择性地抑制 RabGGTase，IC(50) 为 1.3 μM。构效关系分析表明了一个最小结构，涉及地苯丙酮核心与 3-羟基和 4-醛基序，用于与 RabGGTase 结合。RabGGTase:PA 复合物的晶体结构分析表明，PA 与 RabGGTase 的类异戊二烯结合位点形成大量疏水相互作用，并且它共价连接到 α 亚基的 N 末端。我们发现，与其他蛋白质异戊二烯转移酶相比，RabGGTase
• Mechanism of Abietadiene Synthase Catalysis:  Stereochemistry and Stabilization of the Cryptic Pimarenyl Carbocation Intermediates
  作者：Matthew M. Ravn、Reuben J. Peters、Robert M. Coates、Rodney Croteau

  DOI：10.1021/ja017734b

  日期：2002.6.1

  carbocation/OPP anion stabilization of the secondary sandaracopimaren-15-yl(+) ion. The failure of 8 beta-hydroxy-17-nor CPP (19b) to undergo enzymatic cyclization was taken as evidence that 9 is bound with a "coplanar" side chain conformation and that the S(N)' cyclization occurs on the 17 alpha face. The routing of the sandarcopimara-15-en-8-yl carbocation toward various diterpenes in biogenetic schemes

  松香二烯合酶 (AS) 催化 (E,E,E)-香叶基香叶基二磷酸 (8, GGPP) 复杂的环化重排形成松香二烯 (1a)、双键异构体 2a-4a 和海蜇二烯 5a-7a 的混合物针叶树油树脂的松香烷树脂酸成分 (1b-4b) 的生物合成步骤。反应通过中间体二磷酸共苯酯 (9) 在两个活性位点进行。在第二个位点中，形成了未定义的 C13 立体化学和环状双键位置的推定三环海茚二烯或芴基（+）碳阳离子中间体。合成了 9 的三种 8-oxy-17-nor 类似物（17 和 19a,b）和三种异构体 15,16-双去甲蒎烯基-N-甲胺（26a-c）作为替代底物和/或抑制剂用于重组 AS大冷杉。8 α-羟基-17-nor CPP (19a) 到 17-normanoyl 氧化物 (20a) 的立体有择环化和去甲芘胺 26a 的更高抑制效力 (K(i) = 0.1 nM) 都表明具有 13 β甲基构型和
• Sesquiterpene Synthases Cop4 and Cop6 from Coprinus cinereus: Catalytic Promiscuity and Cyclization of Farnesyl Pyrophosphate Geometric Isomers
  作者：Fernando Lopez-Gallego、Sean A. Agger、Daniel Abate-Pella、Mark D. Distefano、Claudia Schmidt-Dannert

  DOI：10.1002/cbic.200900671

  日期：——

  Cyclization of FPP: Two new fungal sesquiterpene synthase are described that have opposite catalytic fidelities in the cyclization of farnesyl diphosphate. Catalytic promiscuity can be drastically reduced by changing the conditions of the reaction. Conversion of the FPP geometric isomers was found to proceed via opposite enantiomers of a cyclic carbocation intermediate that are rearranged to different

  FPP 的环化：描述了两种新的真菌倍半萜烯合酶，它们在二磷酸法呢酯的环化中具有相反的催化保真度。通过改变反应条件可以大大减少催化混杂。发现 FPP 几何异构体的转化是通过环状碳阳离子中间体的相反对映异构体进行的，这些对映异构体重新排列成不同的倍半萜烯产物。
• Mechanisms of the Diterpene Cyclases β-Pinacene Synthase from<i>Dictyostelium discoideum</i>and Hydropyrene Synthase from<i>Streptomyces clavuligerus</i>
  作者：Jan Rinkel、Patrick Rabe、Xinlu Chen、Tobias G. Köllner、Feng Chen、Jeroen S. Dickschat

  DOI：10.1002/chem.201702704

  日期：2017.8.4

  Two diterpene cyclases, one from the social amoeba Dictyostelium discoideum and the other from the bacterium Streptomyces clavuligerus, with products containing a Z‐configured double bond between the original C2 and C3 of geranylgeranyl diphosphate, were extensively investigated for their mechanisms through isotopic labelling experiments. The participation of geranyllinalyl diphosphate, in analogy

  两种双萜环化酶，一种来自社交变形虫盘基网柄菌，另一种来自细菌链霉菌，其产物在二磷酸香叶基香叶基二磷酸的原始C2和C3之间含有Z构型的双键，通过同位素标记实验对其机理进行了广泛研究。讨论了草甘膦基二磷酸二酯的参与，类似于芳基二磷酸和神经节苷脂在单萜和倍半萜生物合成中的作用，它是形成具有Z构型的C2 = C3双键的二萜的中间体。