共查询到20条相似文献,搜索用时 31 毫秒
1.
The reaction of p-tert-butylcalix[8]arene with PCl5, followed by hydrolysis and subsequent esterification with triethyl orthoformate afforded a triphosphate involving all phenolic oxygen atoms of the calixarene framework. As revealed by an X-ray diffraction study, the presence of two μ3-(O,O,O) and one μ2-(O,O) bridging phosphoryl groups results in an unusual lengthening of the calix[8]arene loop (longest OO separation: 13.9 Å) 相似文献
2.
IntroductionAcetolactatesynthase(ALS)isthefirstcommonenzymeinthebiosyntheticpathwayforthebranched-chainaminoacidsvaline,leucineandisoleucine.Itisaveryeffectivetargetsiteforherbicidalaction,whichistheselectedmodeofactionasitisspecificforplantsanddoesnotaffectmammals.Sulfonylureaherbicidesareanewclassofherbicidesdiscoveredinthemid-l97O'sl.ItsmodeofactionhasbeenestablishedtobeinhibitorytowardALS2.Muchattentionhasbeenfocusedonthiskindofcompounds,sincetheyhaveexcellentactivity,ahighdegreeofseIe… 相似文献
3.
Gao X Zhu G Zeng Z Chen W Lin Z Liu Y Xu P Zhao Y 《Rapid communications in mass spectrometry : RCM》2011,25(8):1061-1069
The mass spectral behavior of amino acid methyl ester phosphoramidate derivatives have been investigated using electrospray ionization multistage mass spectrometry (ESI-MS(n)) and moderate theoretical calculations at the B3LYP/6-31G(d) level. A novel methyl group migration to the phosphoryl group with the formation of the intermediate cyclic aminoacylphosphoramidate was found. The proposed structures of the rearrangement ions were confirmed by high-resolution tandem mass spectrometry. A possible mechanism involving the pentacoordinate phosphoric-carboxylic phosphate anhydride was proposed, in which the metal ion coordination with the phosphoryl and carbonyl groups and the intrinsic properties of phosphoryl group might be the key factors responsible for this novel migration. 相似文献
4.
In this report, the dipolarophile imines with easily removable activating group O,O-diethyl(thio)phosphoryl have been investigated in the nucleophilic phosphine-catalyzed [3+2] cycloaddition reaction of electron-deficient allenes. Under the catalysis of a tertiary phosphine, N-(thio)phosphorylimines readily undergo the [3+2] cycloaddition reaction with ethyl 2,3-butadienoate or ethyl 2,3-pentadienoate, affording the corresponding N-(thio)phosphoryl 3-pyrrolines in moderate to high yields with good diastereoselectivity. Removal of the (thio)phosphoryl group from the adducts has been successfully achieved via the acidic methanolysis of the P-N bond, giving the free amine 3-pyrrolines in fair to good yields without severe aromatization. Thus, a facile synthesis of N-unsubstituted 3-pyrrolines is established from the phosphine-catalyzed [3+2] cycloaddition reaction of allenes with imines. 相似文献
5.
Phosphoryl amino acids and their analogues are continuing to be increasingly important as potential enzyme inhibitors, mechanistic probes for proteases[1,2]. Previously, a series of investigations on the structure-reactivity relationship about phosphoryl amino acids 1 had been carried out, the results showed that the co-participation of phosphoryl group, carboxyl group and residues of amino acids were essential and their biomimic reaction mechanisms were commonly through a penta-coordinate intramolecular mixed carboxylic-phosphoric anhydride intermediates[3]. 相似文献
6.
The polymers containing ribose rings: poly(5'-acrylamido-5'-deoxy-1',2'-O-isopropylidene-alpha-D-ribose) (11), poly(5'-acrylamido-5'-deoxy-alpha-D-ribose) (12) and poly(5'-acrylamido-5'-deoxy-1'-O-methyl-D-ribose) (13) were prepared as enzyme mimics. Polymers 12 and 13 with free vic-cis-diol groups catalyzed the hydrolysis of phosphodiester (ethyl p-nitrophenyl phosphate and N-methylpyridinium 4-tert-butylcatechol cyclic phosphate) and phosphomonoester substrates with a rate acceleration of 10 approximately equal to 10(3) compared with the uncatalyzed reaction. They also catalyzed the reverse reactions, i.e., the esterification of phosphomonoester to phosphodiester and the phosphorylation of alcohols with phosphate ions. The catalytic activity was attributable to the vic-cis-diols of riboses on polymer chains, which formed hydrogen bonds with two phosphoryl oxygen atoms of phosphates so as to activate the phosphorus atoms to be attacked by nucleophiles. The catalytic activity was negligible for polymer 11 where vic-cis-diol groups were blocked with isopropylidene groups. The catalytic activity was attributable to the vic-cis-diols of riboses on polymer chains, which formed hydrogen bonds with two phosphoryl oxygen atoms of phosphates so as to activate the phosphorus atoms to be attacked by nucleophiles. 相似文献
7.
In view of the isosterism of the sulfonyl group(‐SO2‐) and the phosphoryl group, two new types of compounds N‐(N‐aryl‐O‐alkyl phosphoryl)‐N′‐(4,6‐dimethoxypyrimidin‐2‐yl) ureas (2) and N‐(N‐aryl‐N‐alkylphosphoryl)‐N′‐(4,6‐dimethoxypyrimidin‐2‐yl) ureas (3) were designed and synthesized by treating N‐(arylaminochlorophosphoryl)‐N′‐(4,6‐dimethoxypy‐rimidinyl‐2‐) ureas (4) with alcohols or amines. Compounds 4 were obtained by treating dichloro‐phosphoryl isocyanate with 4,6‐dimethoxy‐2‐amino‐pyrimidine and then with aromatic amines. The enzyme tests in vitro indicated that compounds 2 and 3 were two novel classes of acetolactate synthase (ALS) inhibitors and also showed that phosphoryl groups[‐P(O)(OR)‐, R=alkyl] and [‐P(O)(NHR), R=alkyl] were likely to be good bioisosteres of the sulfonyl group (‐SO2‐) in the sulfonylureas. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10:237–241, 1999 相似文献
8.
Cui J Gao X Fan A Zhang S Liu Y Xu P Zhao Y 《European journal of mass spectrometry (Chichester, England)》2011,17(2):187-195
Several amino acid phosphorodiamidate derivatives of d4T as anti-HIV prodrugs were synthesized and investigated using electrospray ionization multistage tandem mass spectrometry (ESI-MS(n)). A novel methyl group migration in gas phase was observed in ESI-MS(2) of the sodium adducts of amino acid methyl ester of phosphorodiamidates of 2',3'-didehydro-2',3'-dideoxythymidine (d4T). The proposed structures of the rearrangement ions were confirmed by high resolution tandem mass spectrometry. A possible mechanism involving the pentacoordinate phosphoric-carboxylic phosphate anhydride was proposed, in which a seven-membered ring intermediate was formed by coordination with the metal ion between the phosphoryl group and carbonyl oxygen atom. Thus, the intrinsic properties of phosphoryl group might be the key factors responsible for this migration. 相似文献
9.
Evidence is presented for the view that acid-catalyzed esterification of the carboxyl group of o-hydroxyphenoxyacetic acid is facilitated by the neighboring phenolic hydroxyl group, and that the facilitated esterification proceeds via formation of the intermediate γ-lactone. 相似文献
10.
Phosphoryl transfer is a key reaction in many aspects of metabolism, gene regulation, and signal transduction. One prominent example is the phosphoenolpyruvate:sugar phosphotransferase system (PTS), which represents an integral part of the bacterial sugar metabolism. The transfer between the enzymes IIA (Glc) and IIB (Glc) in the glucose-specific branch of the PTS is of particular interest due to the unusual combination of donor and acceptor residues involved in phosphoryl transfer: The phosphoryl group is initially attached to the Nepsilon2 atom of His 90 in IIA (Glc) and then transferred to the S gamma atom of Cys 35 in IIB (Glc). To gain insight into the details of the transfer mechanism, we have performed a QM/MM simulation which treats the entire active site quantum-mechanically. The transfer has a high dissociative character, and the Nepsilon2-P bond gets immediately destabilized after complex formation by numerous interactions formed between residues of IIB (Glc) and the phosphoryl group. The final formation of a tight S gamma-P bond is accompanied by a reorientation of the side chain of the phosphoryl donor. This reorientation results in the loss of interaction between the imidazole ring and the phosphate group thus hindering the reverse transfer. A comparison to the transfer in protein tyrosine phosphatases, which also use a cysteine as acceptor of the phosphoryl group, reveals significant similarities in the conformation of the active site, the energy profile of the reaction, and in the pattern of interactions that stabilize the phosphoryl group during the transfer. 相似文献
11.
Webster CE 《Journal of the American Chemical Society》2004,126(22):6840-6841
A recent crystal structure of beta-phosphoglucomutase from Lactococcus lactis is reported to contain a five-coordinate phosphorus with five oxygen ligands that is a high-energy reaction intermediate during the phosphoryl transfer in the isomerization of beta-glucose 1-phosphate to beta-glucose 6-phosphate. Subsequently, it has been suggested that this structure is a transition state analogue with a five-coordinate magnesium with two oxygen and three fluorine ligands. Two layer ONIOM(B3LYP:PM3MM) calculations have been performed to address the nature of this intermediate and the mechanism of the phosphoryl transfer. These calculations provide evidence that (1) the observed crystal structure is consistent with a five-coordinate magnesium (a stable transition state analogue), not a five-coordinate phosphorus (a phosphorane) as a high-energy intermediate, (2) the active site is stabilized by the extensive hydrogen-bonding network, (3) the transfer of the phosphoryl group proceeds through a moderate barrier (14 kcal mol-1) five-coordinate phosphorus without a stable phosphorane or metaphosphate intermediate, (4) this concerted transition state is directly coupled to a proton transfer from the oxygen of glucose to the carboxylic group of aspartate 10, and (5) a stable glucose 1,6-bis-phosphoglucose intermediate is formed. 相似文献
12.
Katie Ruffell Dr. Frances R. Smith Michael T. Green Dr. Simon M. Nicolle Dr. Martyn Inman Dr. William Lewis Prof. Dr. Christopher J. Hayes Prof. Dr. Christopher J. Moody 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(55):13703-13708
Diazophosphonates, readily prepared from α-ketophosphonates by oxidation of the corresponding hydrazones in batch or in flow, are useful partners in 1,3-dipolar cycloaddition reactions to alkynes to give N-H pyrazoles, including the first intramolecular examples of such a process. The phosphoryl group imbues a number of desirable properties into the diazo 1,3-dipole. The electron-withdrawing nature of the phosphoryl stabilizes the diazo compound making it easier to handle, whilst the ability of the phosphoryl group to migrate readily in a [1,5]-sigmatropic rearrangement enables its transfer from C to N to aromatize the initial cycloadduct, and hence its facile removal from the final pyrazole product. Overall, the diazophosphonate acts as a surrogate for the much less stable diazoalkane in cycloadditions, with the phosphoryl group playing a vital, but traceless, role. The cycloaddition proceeds more readily with alkynes bearing electron-withdrawing groups, and is regiospecific with asymmetrical alkynes. The potential of diazophosphonates for use in bioorthogonal cycloadditions is demonstrated by their facile addition to strained alkynes. 相似文献
13.
Amino acid methyl ester phosphates were synthesized and determined by using positive-ion mode electrospray ionization mass spectrometry(ESIMS) in combination with multistage tandem mass spectrometry. The fragmentation pathways were investigated, and it was observed that most fragment ions contained the phosphoryl group. It was interesting to observe that the fragmentation pathways of the protonated molecule show some differences when compared with those of the sodium ion adduct. The methoxy group of amino acid methyl ester can migrate from the carbonyl group to the phosphoryl group in the sodium ion adduct. 相似文献
14.
CHEN Wei-zhu GAO Yu-xing BAI Yong-gang HAN Da-xiong ZHAO Yu-fen 《高等学校化学研究》2006,22(6):732-737
Amino acid methyl ester phosphates were synthesized and determined by using positive-ion mode dectrospmy ionization mass spectrometry(ESIMS) in combination with multistage tandem mass spectrometry. The fragmentation pathways were investigated, and it was observed that most fragment ions contained the phosphoryl group. It was interesting to observe that the fragmentation pathways of the protonated molecule show some differences when compared with those of the sodium ion adduct. The methoxy group of amino acid methyl ester can migrate from the carbonyl group to the phosphoryl group in the sodium ion adduct. 相似文献
15.
16.
Bekim Bajrami Yu Shi Pascal Lapierre Xudong Yao 《Journal of the American Society for Mass Spectrometry》2009,20(11):2124-2134
Ions near the high-end border of a mass defect distribution plot for native peptide fragment ions have potential as signature
markers that are based on mass-to-charge ratio determination. The specificity of these marker ions, including phosphoryl ions,
can be improved by removing interfering isobaric ions from the border region on the distribution plot. These interfering ions
are rich in Asp and Glu content. The masses of amino acid residues and peptides are rescaled from the IUPAC scale (12C=12 u as the mass reference) to the averagine scale (averagine mass=111 u* as the mass reference with zero mass defect; u*:
the mass unit on the averagine scale), using a scaling factor of 0.999493894. It is theoretically predicted that esterification
of Asp and Glu side-chain carboxylates with n-butanol can achieve a sufficient retreat of the high-end border on a mass defect distribution plot based on the use of mass
spectrometers with better-than-medium resolution. Theoretical calculations and laboratory experiments are performed to examine
effects of various esterifications on the averagine-scale mass defect distribution of peptide fragment ions and on the specificity
of two positive phosphoryl ions: the phosphotyrosine immonium ion and a cyclophosphoramidate ion. 相似文献
17.
《高等学校化学研究》2006,(6)
IntroductionIn recent years, nucleosides and their analogshave been extensively studied as potential anticancerand antiviral agents[1—3]. For example, several purineand pyridine bases and nucleoside analogs are used aschemotherapeutic arsenal. For their biological activity,these analogs should be intracellularly metabolized to5′-mononucleotides by kinase-mediated phosphoryla-tion[4]. To overcome the problemof drug resistance andto improve the membrane penetration, a series of aminoacid phosp… 相似文献
18.
Orazio A. Attanasi Graziano Baccolini Lucia De Crescentini Paolino Filippone 《Tetrahedron》2008,64(28):6724-6732
The reaction of 1,2-diaza-1,3-butadienes with dialkyl phenylphosphonites under solvent-free conditions proceeds via zwitterionic intermediate and gives, by precipitation, the stable ylidic α-phosphanylidene-hydrazones that, in turn, can be transformed into the corresponding 3-phenyl-2H-1,2,3λ5-diazaphospholes. The latter compounds are converted by hydrolytic cleavage in methanol-water (95:5) into E-hydrazonophosphonates that are useful for the preparation of the corresponding β-ketophosphonates and 4-[alkoxy(phenyl)phosphoryl]-1,2-diaza-1,3-butadienes. These peculiar 1,2-diaza-1,3-butadienes, bearing an alkoxy(phenyl)phosphoryl group on the carbon atom in position 4 are also able to add different nucleophiles, such as methanol or thiourea, giving 2-[alkoxy(phenyl)phosphoryl]-2-methoxyhydrazones and 5-phosphinate-substituted thiazol-4-ones, respectively. 相似文献
19.
一种含P-N键的双环磷酸酯化合物的合成及晶体结构 总被引:6,自引:0,他引:6
合成了 1种双环磷酸酯 磷酰胺类阻燃剂——— 1 ,2 二 (2 氧代 5,5 二甲基 1 ,3,2 二氧磷杂环己 2 氨基 )乙烷 [BPEA](C1 2 H2 6N2 O6P2 ,Mr=356.2 9) ,用X 射线衍射法、红外光谱和1 HNMR表征了该化合物。晶体学数据为 :单斜晶系 ,空间群P2 1 /n ,a =6.9657(1 0 ) ,b =1 4 571 (3) ,c =8.642 6(1 2 ) ;β =91 .1 91 (1 1 )°;V =877.0 (2 ) 3,Z =2 ,Dc=1 .349g/cm3,μ =0 .2 76mm- 1 ,F(0 0 0 ) =380。结构由直接法解出 ,用全矩阵最小二乘法修正 ,最终偏离因子R =0 .0 4 0 5,wR =0 0 890 (I >2σ(I) )的可观测衍射 1 354个。BPEA的晶体结构表明 ,它是通过乙二胺联系的 2个六员环构成并以对称中心分布。 相似文献
20.
合成了两种膦酰基离子液体,1-丁基-3-(3-二苯基膦酰基)丙基咪唑六氟磷酸盐([BIMC3P(O)Ph2]PF6)(IL-1)和(3-二苯基膦酰基)-丙基三乙胺六氟磷酸盐([TEAC3P(O)Ph2]PF6)(IL-2),通过核磁共振和红外光谱确认了它们的结构,并合成了两种离子液体的稀土铕配合物Eu(IL-1)3(NO3)3和Eu(IL-2)3(NO3)3,对其进行了热稳定性和光谱性质的表征。 热重分析表明,离子液体的热稳定性均高于其稀土配合物,相比之下,离子液体IL-1和Eu(IL-1)3(NO3)3具有更好的热稳定性。 从红外光谱中可以看出,形成配合物后,两种离子液体中的P=O吸收峰均向低波数方向移动,同时两种配合物的紫外吸收强度均大于各自游离的离子液体,说明Eu3+和离子液体中的磷酰基发生了配位。 稀土铕配合物Eu(IL-1)3(NO3)3和Eu(IL-2)3(NO3)3的荧光光谱均表现出Eu3+的特征红光,峰形尖锐,单色性好,可作为潜在的红色发光材料。 相似文献