5754-34-7Relevant articles and documents
First total synthesis of isoprostane IPF(2α)-III
Adiyaman, Mustafa,Li, Hongwei,Lawson, John A.,Hwang, Seong-Woo,Khanapure, Subhash P.,FitzGerald, Garret A.,Rokach, Joshua
, p. 3339 - 3342 (1997)
The first total synthesis of IPF(2α)-III, a type III isoprostane is described using a syn-anti-syn lactone 34 prepared from D-glucose and a novel iodohydrin synthon 30. This is first synthesis of a representative of type III isoprostane which is anticipated to be formed in vivo from arachidonic acid by free-radical mechanism. This synthetic material will help elucidate the formation in vivo of type III isoprostanes.
iPF2α-III-17,18,19,20-d4: Total synthesis and metabolism
Kim, Seongjin,Powell, William S.,Lawson, John A.,Jacobo, Sheila H.,Pratico, Domenico,FitzGerald, Garret A.,Maxey, Kirk,Rokach, Joshua
, p. 1613 - 1617 (2005)
The first total synthesis of 17,18,19,20-d4-iPF 2α-III 32, a deuterated analog of iPF2α-III, is described. We have used this analog in some β-oxidation studies with rat liver homogenates and have shown that 32 was metabolized to 17,18,19,20-tetradeutero-2,3-dinor-iPF2α-III 36 and 17,18,19,20-tetradeutero-2,3-dinor-5,6-dihydro-iPF2α-III 37.
Sulfones as Synthetic Linchpins: Transition-Metal-Free sp3–sp2 and sp2–sp2 Cross-Couplings Between Geminal Bis(sulfones) and Organolithium Compounds
Trost, Barry M.,Kalnmals, Christopher A.
supporting information, p. 9066 - 9074 (2018/06/29)
A valuable umpolung strategy that highlights the ambiphilic nature of the bis(phenylsulfonyl)methyl synthon and demonstrates its utility as a synthetic linchpin is reported. Although the bis(phenylsulfonyl)methyl group is typically introduced as an sp3-carbon nucleophile, it is demonstrated that it can also function as an effective sp2-carbon electrophile in the presence of organolithium nucleophiles. Alkyl- and aryllithiums couple with the central carbon of the bis(phenylsulfonyl)methyl unit to ultimately generate trisubstituted alkenes, comprising formal sp3–sp2 and sp2–sp2 cross-couplings between organolithium reagents and bis(sulfones). This process occurs almost instantaneously at ?78 °C in the absence of any transition metals. By developing this curious transformation, it has been demonstrated that bis(phenylsulfonyl)methane is a valuable synthetic linchpin, which can undergo two C?C bond-forming processes as an sp3-nucleophile, followed by a third C?C bond-forming reaction as an effective sp2-electrophile. This discovery significantly enhances the utility of this ubiquitous, but underutilized, linker group.
Condensation of 1,2,4-Butanetriol with Carbonyl Compounds and Reactions of Hydroxyalkyl-1,3-dioxacyclanes
Raskil’dina,Borisova, Yu. G.,Zlotskii
, p. 1601 - 1605 (2018/11/10)
A mixture of isomers of 2-(1,3-dioxolan-4-yl)ethanol and 1,3-dioxan-4-ylmethanol was prepared by reaction of 1,2,4-butanetriol with paraformaldehyde. This mixture was subjected to O-alkylation, O-acylation, condensation with phenyl isocyanate, and substitution of OH groups for Cl. The relative activity of acetone derivatives of glycerol and 1,2,4-butanetriol in reactions with allyl chloride and benzyl chloride was estimated.
Cobalt versus Osmium: Control of Both trans and cis Selectivity in Construction of the EFG Rings of Pectenotoxin 4
Roushanbakhti, Ahria,Liu, Yifan,Winship, Paul C. M.,Tucker, Michael J.,Akhtar, Wasim M.,Walter, Daryl S.,Wrigley, Gail,Donohoe, Timothy J.
supporting information, p. 14883 - 14887 (2017/10/24)
Catalytic oxidative cyclisation reactions have been employed for the synthesis of the E and F rings of the complex natural product target pectenotoxin 4. The choice of metal catalyst (cobalt- or osmium-based) allowed for the formation of THF rings with either trans or cis stereoselectivity. Fragment union using a modified Julia reaction then enabled the synthesis of an advanced synthetic intermediate containing the EF and G rings of the target.
Identification of a Water-Soluble Indirubin Derivative as Potent Inhibitor of Insulin-like Growth Factor 1 Receptor through Structural Modification of the Parent Natural Molecule
Cheng, Xinlai,Merz, Karl-Heinz,Vatter, Sandra,Zeller, Jochen,Muehlbeyer, Stephan,Thommet, Andrea,Christ, Jochen,W?lfl, Stefan,Eisenbrand, Gerhard
supporting information, p. 4949 - 4962 (2017/06/28)
Indirubins have been identified as potent ATP-competitive protein kinase inhibitors. Structural modifications in the 5-and 3′-position have been extensively investigated, but the impact of substituents in 5′-position is not equally well-studied. Here, we report the synthesis of new indirubin 3′-and 5′-derivatives in the search of water-soluble indirubins by introducing basic centers. Antiproliferative activity of all compounds in tumor cells was evaluated along with kinase inhibition of selected compounds. The results show the 3′-position to tolerate large substituents without compromising activity, whereas bulk and rigid substituents in 5′-position appear unfavorable. Screening molecular targets of water-soluble 3′-oxime ethers revealed 6ha as preferential inhibitor of insulin-like growth factor 1 receptor (IGF-1R) in a panel of 22 protein kinases and in cells. Consistently, 6ha inhibited tumor cell growth in the NCI 60 cell line panel and induced apoptosis. The results indicate that the 5′-position provides limited space for chemical modifications and identify 6ha as a potent water-soluble indirubin-based IGF-1R inhibitor.
Intramolecular thermal stepwise [2 + 2] cycloadditions: Investigation of a stereoselective synthesis of [n.2.0]-bicyclolactones
Throup, Adam,Patterson, Laurence H.,Sheldrake, Helen M.
supporting information, p. 9554 - 9559 (2016/10/22)
Fused cyclobutanes are found in a range of natural products and formation of these motifs in a straightforward and easy manner represents an interesting synthetic challenge. To this end we investigated an intramolecular variant of the thermal enamine [2 + 2] cyclisation, developing a diastereoselective intramolecular enamine [2 + 2] cyclisation furnishing δ lactone and lactam fused cyclobutenes in good yield and excellent diastereoselectivity.
High-selectivity ratio fluorescence probe for detecting periodate radicals
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Paragraph 0089; 0090; 0091; 0092, (2016/10/27)
The invention provides a high-selectivity ratio fluorescence probe for detecting periodate radicals. The probe has a structure represented by formula I. In the formula I, R1 is selected from H or C1-C4 alkyl groups; R2 is selected from C2-C8 alkyl groups with two adjacent carbon atoms respectively being substituted by one hydroxyl group; R3 is selected from H and C1-C4 alkyl groups; and R4 is selected from H and C1-C4 alkyl groups. The invention also provides an intermediate compound represented by formula II and used for preparing the compound of the formula I, a preparation method of the compound of the formula I, a detection composition containing the compound of the formula I, a detection kit containing the compound of the formula I, and an application of the compound of the formula I in detection of the periodate radicals in a chemical system, fluorescence imaging test of the periodate radicals in biological living cells, construction of high-flux hydrolase test platforms, and exploitation of detection test strips as a fluorescence probe.
Synthesis of DOHNAA, a Mycobacterium tuberculosis Cholesterol CD Ring Catabolite and FadD3 Substrate
Stubbing, Louise A.,Lott, J. Shaun,Dawes, Stephanie S.,Furkert, Daniel P.,Brimble, Margaret A.
, p. 6075 - 6083 (2015/09/22)
DOHNAA (2) is a key catabolite in the Mycobacterium tuberculosis (Mtb) cholesterol degradation pathway. The CoA ester of 2 has been implicated in regulation of gene transcription that is ultimately responsible for degradation of the C and D rings of cholesterol. A synthetic route to 2 is reported here, by a key DMSO-mediated Morita-Bayliss-Hillman-type alkylation of the Hajos-Parrish dione. As DOHNAA has to date only been available from microbial sources in very small quantities, the synthesis described will enable further studies of the enzymes involved in cholesterol degradation in Mtb and facilitate ongoing structure-activity studies based on this compound scaffold.
NOVEL ENERGETIC POLYPHOSPHAZENES
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Page/Page column 7, (2012/03/12)
This invention describes the synthesis and use of novel energetic poly(phosphazene) materials suitable for binding high explosives. These materials may also be used as explosives in their own right. The materials possess high energy density and are highly amenable to chemical modification thereby allowing for modification to the physical properties of the material. In particular the tacky and rubbery nature of these materials makes them ideal for use as binder and co-binder materials.
