tetra-n-butylammonium dimethyl phosphate

• 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: tetra-n-butylammonium dimethyl phosphate
• 英文别名: tetrabutylammonium dimethyl phosphate；4-((3-Bromophenyl)sulfonyl)-N-(1-(thiophen-2-yl)ethyl)piperazine-1-carboxamide；dimethyl phosphate;tetrabutylazanium
• 化学式: C₂H₆O₄P*C₁₆H₃₆N
• 分子量: 367.51
• InChiKey: OGNAJHOXQVGXLZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.75
• 重原子数：
  24
• 可旋转键数：
  14
• 环数：
  0.0
• 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：

  二甲基硫代磷酰氯 、 tetra-n-butylammonium dimethyl phosphate 在 4-二甲氨基吡啶 作用下， 以 乙腈 为溶剂， 反应 0.5h， 以53%的产率得到四甲基焦磷酸硫代酸酯
  参考文献：
  名称：

  了解并改造葎草烯合酶的立体选择性

  摘要：

  非经典萜烯环化酶 AsR6 负责在托酚酮倍半萜 (TS) 异戊烯 A 生物合成过程中形成 2 E ,6 E ,9 E -葎草烯。未配体 AsR6 和与晶体复合的 AsR6 的结构环化反应产物和硫代二磷酸揭示了一个新的法呢基二磷酸结合基序，该基序包含独特的双核 Mg 2+簇和重要的 K289 残基，该残基在参与 TS 形成的所有葎草烯合酶中都是保守的。AsR6 及其同源物 EupR3 的基于结构的定点诱变鉴定出单个残基 L285/M261，其控制 2 E ,6 E ,9 E - 或 2 Z ,6 E ,9 E -humulene的产生。使用不同的类异戊二烯前体研究了观察到的立体选择性的可能机制，结果表明 M261 对产物形成具有把关控制作用。

  DOI：

  10.1002/anie.202106718
• 作为产物：
  描述：

  磷酸三甲酯 、 四丁基碘化铵 在 溶剂黄146 作用下， 反应 15.0h， 以96%的产率得到tetra-n-butylammonium dimethyl phosphate
  参考文献：
  名称：

  改变季鎓卤化物中阴离子的有效方法

  摘要：

  卤化物季鎓盐可高效转化为相应的各种阴离子季鎓盐[NO3-、BF4-、PF6-、CF3SO3-、CH3SO3-、ClO4-、p-CH3C6H4SO3-、CF3CO2-、2,4-( NO2)2C6H3O-] 在等量的所需阴离子共轭酸存在下，在纯净条件下用磷酸三甲酯处理卤化鎓。

  DOI：

  10.1002/ejoc.201200370
• 作为试剂：
  描述：

  反式肉桂醛 、 (三氟甲基)三甲基硅烷 在 tetra-n-butylammonium dimethyl phosphate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.17h， 以86%的产率得到trimethyl[[(2E)-3-phenyl-1-(trifluoromethyl)-2-propenyl]oxy]silane
  参考文献：
  名称：

  Facile Synthesis of TMS-Protected Trifluoromethylated Alcohols Using Trifluoromethyltrimethylsilane (TMSCF₃) and Various Nucleophilic Catalysts in DMF

  摘要：

  Organofluorine compounds are becoming increasingly important in different fields, such as material science, agro chemistry, and the pharmaceutical industry. Nucleophilic trifluoromethylation is one of the widely used methods to incorporate a trifluoromethyl moiety into organic molecules. We have carried out extensive studies to develop varieties of easily accessible nucleophilic catalysts to promote such reactions. TMS-protected trifluoromethylated alcohols were prepared from both aldehydes and ketones in excellent yields using catalytic amount of amine N-oxide. Carbonate and phosphate salts also showed efficient catalytic activity toward this reaction. These reactions were highly solvent dependent, and DMF was found to be the most suitable one among the various solvents studied. All these reactions proceeded under very mild conditions, giving clean products and avoiding the use of any fluoride initiators or expensive catalysts, and extremely water-free conditions. The mechanism for the reaction is discussed in detail. DFT calculations were performed on the possible reaction intermediates using the Gaussian 03 program at B3LYP/6-311+G* level to support the proposed mechanism.

  DOI：

  10.1021/jo060835d

文献信息

• PRODRUGS OF FUSED-BICYCLIC C5aR ANTAGONISTS
  申请人：CHEMOCENTRYX, INC.

  公开号：US20190300526A1

  公开（公告）日：2019-10-03

  The present disclosure provides, inter alia, Compounds of Formulae IA, IB, IC, IIA, IIB and IIC or pharmaceutically acceptable salts thereof that are modulators of the C5a receptor. Also provided are pharmaceutical compositions and methods of use including the treatment of diseases or disorders involving pathologic activation from C5a and non-pharmaceutical applications.

  本公开提供了化合物IA、IB、IC、IIA、IIB和IIC的结构，或其在药学上可接受的盐，这些化合物是C5a受体的调节剂。还提供了包括治疗涉及C5a病理性激活的疾病或疾病的药物组合物和使用方法，以及非药物应用。
• Brønsted Base Assisted Photoredox Catalysis: Proton Coupled Electron Transfer for Remote C−C Bond Formation via Amidyl Radicals
  作者：Jiaqi Jia、Yee Ann Ho、Raoul F. Bülow、Magnus Rueping

  DOI：10.1002/chem.201802907

  日期：2018.9.20

  The synthesis of alkyne‐ and alkene‐decorated lactams has been achieved through a photoredox‐initiated radical cascade reaction. The developed Brønsted base assisted, photoredox‐catalyzed, intramolecular 5‐exo‐trig cyclization/intermolecular radical addition/elimination reaction provides facile access to functionalized γ‐lactams, with good functional group tolerance and high yields.

  炔烃和烯烃修饰的内酰胺的合成是通过光氧化还原引发的自由基级联反应实现的。所开发的布朗斯台德碱的帮助下，photoredox催化分子内-5-外- TRIG环化/分子间基加/消除反应提供容易访问官能γ内酰胺类，具有良好的官能团耐受性和高的产率。
• Synthesis and Enzymatic Studies of Isoprenoid Thiolo Bisubstrate Analogues
  作者：Gurusankar Ramamoorthy、Richard M. Phan、C. Dale Poulter

  DOI：10.1021/acs.joc.6b00664

  日期：2016.6.17

  isopentenyl diphosphate (IPP) in the primary building reactions in the isoprenoid biosynthetic pathway. Bis-O-diphosphate analogues 3-OPP/OPP, 4-OPP/OPP, and 5-OPP/OPP and bis-thiolodiphosphate bisubstrate analogues 3-SPP/SPP, 4-SPP/SPP, and 5-SPP/SPP were synthesized. The analogues 4-OPP/OPP, 5-OPP/OPP, 4-SPP/SPP, and 5-SPP/SPP were excellent competitive inhibitors of avian farnesyl diphosphate synthase

  链延长异戊二烯基转移酶在异戊二烯生物合成途径的主要构建反应中，催化将烯丙基异戊二烯二磷酸的烃部分加到异戊烯基二磷酸（IPP）中的碳-碳双键中。双- ø二磷酸类似物3- OPP / OPP，4- OPP / OPP，和5-OPP / OPP和双thiolodiphosphate双底物类似物3-SPP / SPP，4-SPP / SPP，和5-SPP / SPP合成。类似物4-OPP / OPP，5-OPP / OPP，4-SPP / SPP和5-SPP / SPP分别是K I = 1.0±0.12μM，K I = 0.5±0.2μM，K I = 0.7±0.3μM和K I = 2.9±0.27μM的禽法呢基二磷酸合酶的优异竞争抑制剂，而类似物3- OPP / OPP和3-SPP / SPP分别显示了K I = 1.4μM和K I = 5.5μM的混合型抑制。
• A Water‐ and Base‐Stable Iminopyridine‐Based Cage That Can Bind Larger Organic Anions
  作者：Mattias Zenka、Joachim Preinl、Eric Pertermann、Arne Lützen、Konrad Tiefenbacher

  DOI：10.1002/ejic.202300110

  日期：——

  A novel iminopyridine-based Zn4L4 tetrahedral cage, synthesized in four steps, binds larger organic anions with binding constants of up to 850 M−1 in MeCN−d3/H2O=9 : 1 and displays stability in basic aqueous acetonitrile. Surprisingly, investigations towards catalysis of reactions with anionic transition states did not indicate rate accelerations in the presence of the cage.

  一种新型基于亚氨基吡啶的 Zn 4 L 4四面体笼，分四步合成，结合较大的有机阴离子，在 MeCN− d 3 /H 2 O=9 : 1 中具有高达 850 M −1的结合常数，并且在碱性水溶液中表现出稳定性乙腈。令人惊讶的是，对阴离子过渡态反应的催化研究并未表明在笼的存在下速率加速。
• Synthesis of (<i>S</i>)-Isoprenoid Thiodiphosphates as Substrates and Inhibitors
  作者：Richard M. Phan、C. Dale Poulter

  DOI：10.1021/jo010505n

  日期：2001.10.1

  Thiolo thiophosphate analogues of isopentenyl diphosphate (IPP), dimethylallyl. diphosphate (DMAPP), geranyl diphosphate (GPP), farnesyl diphosphate (FPP), and geranylgeranyl diphosphate (GGPP) were synthesized, Inorganic thiopyrophosphate (SPP) was prepared from trimethyl phosphate in four steps. The tris(tetra-n-butylammonium) salt was then used to convert isopentenyl tosylate to (S)-isopentenyl thiodiphosphate (ISPP). (S)-Dimethylallyl (DMASPP), (S)-geranyl (GSPP), (S)-farnesyl (FSPP), and (S)-geranylgeranyl thiodiphosphate (GGSPP) were prepared from the corresponding bromides in a similar manner. ISPP and GSPP were substrates for avian farnesyl diphosphate synthase (FPPase). Incubation of the enzyme with ISPP and GPP gave FSPP, whereas incubation with IPP and GSPP gave FPP. GSPP was a substantially less reactive than GPP in the chain elongation reaction and was an excellent competitive inhibitor, K-I(GSPP) = 24.8 muM, of the enzyme. Thus, when ISPP and DMAPP were incubated with FPPase, GSPP accumulated and was only slowly converted to FSPP.