- Protein Glycosylation through Sulfur Fluoride Exchange (SuFEx) Chemistry: The Key Role of a Fluorosulfate Thiolactoside
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Protein glycosylation is the most complex post-translational modification process. More than 50 % of human cells proteins are glycosylated, whereas bacteria such as E. coli do not have this modification machinery. Indeed, the carbohydrate residues in natural proteins affect their folding, immunogenicity, and stability toward proteases, besides controlling biological properties and activities. It is therefore important to introduce such structural modification in bioengineered proteins lacking the presence of carbohydrate residues. This is not trivial as it requires reagents and conditions compatible with the protein's stability and reactivity. This work reports on the introduction of lactose moieties in two natural proteins, namely ubiquitin (Ub) and l-asparaginase II (ANSII). The synthetic route employed is based on the sulfur(VI) fluoride exchange (SuFEx) coupling of a lactose tethered arylfluorosulfate (Lact-Ar-OSO2F) with the ?-NH2 group of lysine residues of the proteins. This metal-free click SuFEx reaction relies on the properties of the fluorosulfate employed, which is easily prepared in multigram scale from available precursors and reacts chemoselectively with the ?-NH2 group of lysine residues under mild conditions. Thus, iterative couplings of Lact-Ar-OSO2F to Ub and ANSII, afforded multiple glycosylations of these proteins so that up to three and four Lact-Ar-OSO2 groups were introduced in Ub and ANSII, respectively, via the formation of a sulfamoyl (OSO2-NH) linkage.
- Marra, Alberto,Dong, Jiajia,Ma, Tiancheng,Giuntini, Stefano,Crescenzo, Elisa,Cerofolini, Linda,Martinucci, Marco,Luchinat, Claudio,Fragai, Marco,Nativi, Cristina,Dondoni, Alessandro
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Read Online
- Chiral trialkanolamine-based hemicryptophanes: Synthesis and oxovanadium complex
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(Chemical Equation Presented) A novel class of chiral hemicryptophane hosts has been synthesized in diastereoisomerically pure form, namely, M-(R,R,R)-1a/P-(S,S,S)-1a and M-(S,S,S)-1b/P-(R,R,R)-1b. The C 3-symmetrical precursor 9 was prepared, using either (R)- or (S)-glycidyl nosylate, repectively, as the chiral pool reactant and subsequently cyclized (trimerized) in the presence of Sc(OTf)3. The four stereoisomers were fully characterized and displayed two pairs of mirror-image CD spectra, which were used to determine their absolute configuration. The formation of the oxovanadium-(V) complex of hemicryptophane 1a is also reported.
- Gautier, Arnaud,Mulatier, Jean-Christophe,Crassous, Jeanne,Dutasta, Jean-Pierre
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Read Online
- Nickel Hydride Catalyzed Cleavage of Allyl Ethers Induced by Isomerization
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This report discloses the deallylation of O - and N -allyl functional groups by using a combination of a Ni-H precatalyst and excess Bronsted acid. Key steps are the isomerization of the O - or N -allyl group through Ni-catalyzed double-bond migration followed by Bronsted acid induced O/N-C bond hydrolysis. A variety of functional groups are tolerated in this protocol, highlighting its synthetic value.
- Kathe, Prasad M.,Berkefeld, Andreas,Fleischer, Ivana
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supporting information
p. 1629 - 1632
(2021/02/09)
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- Nickel-catalyzed deallylation of aryl allyl ethers with hydrosilanes
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An efficient and mild catalytic deallylation method of aryl allyl ethers is developed, with commercially available Ni(COD)2 as catalyst precursor, simple substituted bipyridine as ligand and air-stable hydrosilanes. The process is compatible with a variety of functional groups and the desired phenol products can be obtained with excellent yields and selectivity. Besides, by detection or isolation of key intermediates, mechanism studies confirm that the deallylation undergoes η3-allylnickel intermediate pathway.
- Ding, Guangni,Fan, Sijie,Wang, Jingyang,Wang, Yu,Wu, Xiaoyu,Xie, Xiaomin,Yang, Liqun,Zhang, Zhaoguo
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supporting information
(2021/09/28)
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- Enantioselective Synthesis of 3-Fluorochromanes via Iodine(I)/Iodine(III) Catalysis
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The chromane nucleus is common to a plenum of bioactive small molecules where it is frequently oxidized at position 3. Motivated by the importance of this position in conferring efficacy, and the prominence of bioisosterism in drug discovery, an iodine(I)/iodine(III) catalysis strategy to access enantioenriched 3-fluorochromanes is disclosed (up to 7:93 e.r.). In situ generation of ArIF2 enables the direct fluorocyclization of allyl phenyl ethers to generate novel scaffolds that manifest the stereoelectronic gauche effect. Mechanistic interrogation using deuterated probes confirms a stereospecific process consistent with a type IIinv pathway.
- Daniliuc, Constantin G.,Gilmour, Ryan,Neufeld, Jessica,Sarie, Jér?me C.,Thiehoff, Christian
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supporting information
p. 15069 - 15075
(2020/06/17)
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- CELL CYCLE PROGRESSION INHIBITOR
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The present invention provides a cell cycle progression inhibitor, a cytostatic agent, and an anticancer agent. The cell cycle progression inhibitor, the cytostatic agent, and the anticancer agent each contains a Hes1 protein-PHB2 protein binding enhancer.
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Paragraph 0086
(2019/09/18)
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- Direct Aryloxylation/Alkyloxylation of Dialkyl Phosphonates for the Synthesis of Mixed Phosphonates
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A strategy for the direct functionalization strategy of inertial dialkyl phosphonates with hydroxy compounds to afford diverse mixed phosphonates with good yields and functional-group tolerance has been developed. Mechanistic investigations involving both NMR studies and DFT studies suggest that an unprecedented highly reactive PV species (phosphoryl pyridin-1-ium salt), a key intermediate for this new synthetic transformation, is generated in situ from dialkyl phosphonate in the presence of Tf2O/pyridine.
- Huang, Hai,Denne, Johanna,Yang, Chou-Hsun,Wang, Haobin,Kang, Jun Yong
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supporting information
p. 6624 - 6628
(2018/05/14)
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- AMINATION AND HYDROXYLATION OF ARYLMETAL COMPOUNDS
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In one aspect, the present disclosure provides methods of preparing a primary or secondary amine and hydroxylated aromatic compounds. In some embodiments, the aromatic compound may be unsubstituted, substituted, or contain one or more heteroatoms within the rings of the aromatic compound. The methods described herein may be carried out without the need for transition metal catalysts or harsh reaction conditions.
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Paragraph 0098; 0226; 0243
(2018/03/25)
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- Combining Orthogonal Chain-End Deprotections and Thiol–Maleimide Michael Coupling: Engineering Discrete Oligomers by an Iterative Growth Strategy
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Orthogonal maleimide and thiol deprotections were combined with thiol–maleimide coupling to synthesize discrete oligomers/macromolecules on a gram scale with molecular weights up to 27.4 kDa (128mer, 7.9 g) using an iterative exponential growth strategy with a degree of polymerization (DP) of 2n?1. Using the same chemistry, a “readable” sequence-defined oligomer and a discrete cyclic topology were also created. Furthermore, uniform dendrons were fabricated using sequential growth (DP=2n?1) or double exponential dendrimer growth approaches (DP=2 22n ?1) with significantly accelerated growth rates. A versatile, efficient, and metal-free method for construction of discrete oligomers with tailored structures and a high growth rate would greatly facilitate research into the structure–property relationships of sophisticated polymeric materials.
- Huang, Zhihao,Zhao, Junfei,Wang, Zimu,Meng, Fanying,Ding, Kunshan,Pan, Xiangqiang,Zhou, Nianchen,Li, Xiaopeng,Zhang, Zhengbiao,Zhu, Xiulin
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supporting information
p. 13612 - 13617
(2017/10/24)
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- Rapid heteroatom transfer to arylmetals utilizing multifunctional reagent scaffolds
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Arylmetals are highly valuable carbon nucleophiles that are readily and inexpensively prepared from aryl halides or arenes and widely used on both laboratory and industrial scales to react directly with a wide range of electrophiles. Although C-C bond formation has been a staple of organic synthesis, the direct transfer of primary amino (-NH2) and hydroxyl (-OH) groups to arylmetals in a scalable and environmentally friendly fashion remains a formidable synthetic challenge because of the absence of suitable heteroatom-transfer reagents. Here, we demonstrate the use of bench-stable N-H and N-alkyl oxaziridines derived from readily available terpenoid scaffolds as efficient multifunctional reagents for the direct primary amination and hydroxylation of structurally diverse aryl- and heteroarylmetals. This practical and scalable method provides one-step synthetic access to primary anilines and phenols at low temperature and avoids the use of transition-metal catalysts, ligands and additives, nitrogen-protecting groups, excess reagents and harsh workup conditions.
- Gao, Hongyin,Zhou, Zhe,Kwon, Doo-Hyun,Coombs, James,Jones, Steven,Behnke, Nicole Erin,Ess, Daniel H.,Kürti, László
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p. 681 - 688
(2017/06/30)
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- Facile conversion of para-benzoquinones to para-alkoxyphenols with primary/secondary alcohols and amberlyst-15: A process showing novel reducing property of such alcohols
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A new efficient methodology has been developed for the synthesis of para-alkoxyphenols, an important group of anti-melanoma compounds, by heating alcoholic solutions of para-benzoquinones in the presence of amberlyst-15. The most notable feature here is the behaviour of the used primary or secondary alcohol as an effective reducing agent.
- Mondal, Rina,Guha, Chayan,Mallik, Asok K.
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supporting information
p. 86 - 89
(2014/01/06)
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- Highly practical iron-catalyzed C-O cleavage reactions
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Facile iron-catalyzed cleavage of various allyl, cinnamyl and benzyl C-O linkages has been effected in the presence of ethylmagnesium chloride. The protocol is operationally simple (xylene-THF, r.t., 1 h), requires low catalyst loading (1 mol% FeCl2) and tolerates halides, esters, amines, ethers and olefins. The allyl moiety is converted to volatile hydrocarbons which renders laborious product separation unnecessary.
- Gaertner, Dominik,Konnerth, Hannelore,Von Wangelin, Axel Jacobi
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p. 2541 - 2545
(2013/09/24)
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- Pd/C-mediated depropargylation of propargyl ethers/amines in water
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Propargyl ethers and amines are effectively depropargylated to the parent alcohols or amines via a C-O/C-N bond cleavage catalyzed by 10% Pd/C in water. This simple, facile, and inexpensive methodology could be utilized for the selective removal of propargyl groups from a variety of aryl ethers and amines.
- Rambabu,Bhavani,Swamy, Nalivela Kumara,Basaveswara Rao,Pal, Manojit
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p. 1169 - 1173
(2013/04/10)
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- Development of β-amino alcohol derivatives that inhibit toll-like receptor 4 mediated inflammatory response as potential antiseptics
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Toll-like receptor 4 (TLR4) induced proinflammatory signaling has been directly implicated in severe sepsis and represents an attractive therapeutic target. Herein, we report our investigations into the structure-activity relationship and preliminary drug metabolism/pharmacokinetics study of β-amino alcohol derivatives that inhibit the TLR4 signaling pathway. Lead compounds were identified from in vitro cellular examination with micromolar potency for their inhibitory effects on TLR4 signaling and subsequently assessed for their ability to suppress the TLR4-induced inflammatory response in an ex vivo whole blood model. In addition, the toxicology, specificity, solubility, brain-blood barrier permeability, and drug metabolism of several compounds were evaluated. Although further optimizations are needed, our findings lay the groundwork for the future drug development of this class of small molecule agents for the treatment of severe sepsis.
- Chavez, Sherry A.,Martinko, Alexander J.,Lau, Corinna,Pham, Michael N.,Cheng, Kui,Bevan, Douglas E.,Mollnes, Tom E.,Yin, Hang
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supporting information; experimental part
p. 4659 - 4669
(2011/09/15)
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- Novel polymeric nonionic photoacid generators and corresponding polymer Langmuir-Blodgett (LB) films for photopatterning
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A series of new polymeric nonionic photoacid generators (PAGs) and PAG-bound polymers designed for photoresist materials in Langmuir-Blodgett (LB) films have been synthesized and characterized. The novel polymer could form a stable and condensed monolayer on water surface, which could be transferred successfully onto solid substrate. Upon deep UV irradiation, the acid generated by the photoacid generator catalyzed the naphthyl moiety to liberate naphthol and regenerate carboxyl in the exposed region. The rent moiety could dissolve in alkaline aqueous, resulting in a fine positive tone resist patterns with a resolution of 0.75 μm. Sensitivity curves and TGA studies revealed that the high sensitivity in 248 nm irradiation was attributed to the present of PAG units incorporated in the polymer chains. The result of translated gold pattern with the same resolution as the resist pattern also demonstrated that the resist LB films had sufficient resistance to wet etching process.
- Xu, Wenjian,Li, Tiesheng,Li, Gaojian,Wu, Yangjie,Miyashita, Tokuji
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experimental part
p. 50 - 57
(2012/01/14)
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- Dialkoxybenzene and dialkoxyallylbenzene feeding and oviposition deterrents against the cabbage looper, trichoplusia ni: Potential insect behavior control agents
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The antifeedant, oviposition deterrent, and toxic effects of individual dialkoxybenzene compounds/sets and of hydroxy- or alkoxy-substituted allylbenzenes, obtained through Claisen rearrangement of substituted allyloxybenzenes, were assessed against the cabbage looper, Trichoplusia ni, in laboratory bioassays. Most of the compounds/sets strongly deterred larval feeding, with some exhibiting mild toxic and oviposition deterrent effects as well. Some of the compounds/sets were more active than the commercial insect repellent, DEET (N,N-diethyl-m-toluamide), as both feeding and oviposition deterrents against the cabbage looper. On the basis of the obtained oviposition data a general hypothesis was proposed regarding the oviposition sites: one binding mode with the alkyl and allyl groups on the same side of the benzene ring resulted in deterrence, the other with alkyl and allyl groups on opposite sides of the benzene ring resulted in stimulation. The results suggest some structure-activity relationships useful in improving the efficacy of the compounds and designing new, nontoxic insect control agents for agriculture.
- Akhtar, Yasmin,Yu, Yang,Isman, Murray B.,Plettner, Erika
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scheme or table
p. 4983 - 4991
(2011/08/06)
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- METHODS AND COMPOSITIONS FOR CONTROL OF GYPSY MOTHS, Lymanria dispar
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The invention provides in part dialkoxybenzene and eugenol compounds for controlling infestation by a Lymantria dispar, and methods thereof. The compounds include a compound of Formula I: where R1 may be methyl, ethyl, propyl, n-butyl, isopentyl (3-methylbutyl) or allyl; R2 may be at positions 2, 3 or 4 and may be H, methyl, ethyl, propyl, n-butyl, isopentyl (3-methylbutyl) or allyl; and R3 may be optionally present at positions 2, 3 and 4, and is allyl; with the provisos that when R2 is at position 2, R3 if present is at position 3, or when R2 is at to position 3, R3 if present is at positions 2 or 4, or when R2 is at position 4, R3 if present is at position 2; or of Formula II: where R1 may be methyl, ethyl, propyl, n-butyl, isopentyl (3-methylbutyl) or allyl; or mixtures thereof.
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Page/Page column 11
(2010/08/07)
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- METHODS AND COMPOSITIONS FOR CONTROL OF CABBAGE LOOPER, Trichoplusia ni
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The invention provides in part dialkoxybenzene compounds for controlling infestation by a Trichoplusia ni, and methods thereof. The compounds include a compound of Formula I: where R1 may be methyl, ethyl, propyl, n-butyl, isopentyl(3-methylbutyl) or allyl; R2 may be at positions 2, 3 or 4 and may be H, methyl, ethyl, propyl, n-butyl, isopentyl(3-methylbutyl) or allyl; and R3 may be optionally present at positions 2, 3 and 4, and is allyl; except that when R2 is at position 2, R3 if present is at position 3, and when R2 is at position 3, R3 if present is at positions 2 or 4, and when R2 is at position 4, R3 if present is at position 2, and when R2 is at position 4 and R3, if present, has reacted with an OH group at position 1 in a Markovnikov sense, then R3 becomes R4, a dihydrofuran.
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Page/Page column 10
(2010/07/04)
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- Design, synthesis and SAR studies of 4-allyoxyaniline amides as potent 15-lipoxygensae inhibitors
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A group of 4-allyloxyaniline amides 5a-o were designed, synthesized and evaluated as potential inhibitors of soybean 15-lipoxygenase (SLO) on the basis of eugenol and esteragol structures. Compound 5e showed the best IC50 in SLO inhibition (IC50 = 0.67 ± 0.06 μM). All compounds were docked in SLO active site retrieved from RCSB Protein Data Bank (PDB entry: 1IK3) and showed that allyloxy group of compounds is oriented towards the Fe3+-OH moiety in the active site of enzyme and fixed by hydrogen bonding with two conserved His513 and Gln716. It is resulted that molecular volume of the amide moiety would be a major factor in inhibitory potency variation of the synthetic amides, where the hydrogen bonding of the amide group could also involve in the activity of the inhibitors.
- Seyedi, Seyed Mohammad,Jafari, Zeinab,Attaran, Neda,Sadeghian, Hamid,Saberi, Mohammad Reza,Riazi, Mohammad Mahdi
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experimental part
p. 1614 - 1622
(2009/08/15)
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- Efficient synthesis of propargylic ethers under the DBU conditions and its application to natural products synthesis
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Conversion of dibromides carrying O-functional groups at adjacent positions to the corresponding propargylic ethers was successfully carried out under the DBU conditions through 2-bromo-1-alkenes as intermediates. The optically active γ-lactone-class natural products, such as (-)-muricatacin (4) and (R,R)-sapinofuranone B (5) were synthesized using the propargylic ether intermediate produced by the elimination reaction mentioned above.
- Yokoyama, Tadashi,Kutsumura, Noriki,Ohgiya, Tadaaki,Nishiyama, Shigeru
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p. 578 - 582
(2008/02/11)
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- ARYLTHIAZOLIDINEDIONE DERIVATIVES
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Substituted 5-aryl-2,4-thiazolidinediones are potent agonists of PPAR, and are therefore useful in the treatment, control or prevention of diabetes, hyperglycemia, hyperlipidemia (including hypercholesterolemia and hypertriglyceridemia), atherosclerosis, obesity, vascular restenosis, and other PPAR alpha , delta and/or gamma mediated diseases, disorders and conditions.
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Page/Page column 34-35
(2010/11/25)
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- New approach to the synthesis of macrocyclic tetralactones via ring-closing metathesis using Grubbs' first-generation catalyst
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(Chemical Equation Presented) A facile and efficient route to synthesize macrocyclic tetralactones with different ring sizes having a wide variety of spacers is described. The application of ring-closing metathesis for the synthesis of macrocyclic tetralactones is demonstrated with many examples in excellent yield. The representative structure of macrocyclic tetralactones is characterized by X-ray crystallography.
- Muthusamy, Sengodagounder,Gnanaprakasam, Boopathy,Suresh, Eringathodi
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p. 1495 - 1498
(2007/10/03)
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- Screening of dialkoxybenzenes and disubstituted cyclopentene derivatives against the cabbage looper, Trichoplusia ni, for the discovery of new feeding and oviposition deterrents
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The antifeedant, oviposition deterrent, and toxic effects of dialkoxybenzene minilibraries and of disubstituted cyclopentene minilibraries (i.e., consisting of four to five compounds) along with their pure constituent compounds were assessed against third instar larvae and adults of the cabbage looper, Trichoplusia ni, in laboratory bioassays in a search for new insect control agents. These compounds mimic naturally occurring bioactive odorants and tastants and are relatively easily prepared from commodity chemicals. Most of these libraries strongly deterred larval feeding, with some exhibiting strong toxic and oviposition deterrent effects as well. Our results suggest some structure-function relationships within these libraries. Replacement of a methyl group with larger alkyl substituents increased the feeding deterrent effects in most cases. The presence of a free hydroxyl group, irrespective of the carbon framework or alkyl substituent, served to reduce feeding deterrent effects in all series of compounds. Further, exceeding a certain group size also generally had a detrimental effect. This information will be useful in designing new insect control agents for agriculture. Some of these libraries and compounds may have potential for development as commercial insecticides.
- Akhtar, Yasmin,Isman, Murray B.,Paduraru, Peggy M.,Nagabandi, Srinivas,Nair, Ranjeet,Plettner, Erika
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scheme or table
p. 10323 - 10330
(2009/10/02)
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- Selective cleavage of allyl and propargyl ethers to alcohols catalyzed by Ti(O-i-Pr)4/MXn/Mg
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(Chemical Equation Presented) Allyl and propargyl ethers were effectively deallylated or depropargylated to the parent alcohols via a C-O bond cleavage catalyzed by a low-valent titanium reagent (LVT), Ti(O-i-Pr)4/TMSCI/ Mg or Ti(O-i-Pr)4/MgBr2/Mg, under mild reaction conditions. Differentiation between the allyl and propargyl ethers was achieved by the reaction in the presence of AcOEt as an additive. The reagent also catalyzed intra- and intermolecular cyclotrimerization reactions of alkynes to substituted benzenes.
- Ohkubo, Mutsumi,Mochizuki, Sayaka,Sano, Takeshi,Kawaguchi, Yuuki,Okamoto, Sentaro
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p. 773 - 776
(2007/10/03)
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- Synthesis of a 10,000-membered library of molecules resembling carpanone and discovery of vesicular traffic inhibitors
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Split-and-pool synthesis of a 10,000-membered library of molecules resembling the natural product carpanone has been achieved. The synthesis features development of solid-phase multicomponent reactions between nitrogen nucleophiles, enones, and hydroxylamines, and a solid-phase application of the Huisgen cycloaddition affording substituted triazoles. The synthesis was performed in high-capacity (500 μm) polystyrene beads using a one bead-one stock solution strategy that enabled phenotypic screens of the resulting library. Using whole-cell fluorescence imaging, we discovered a series of molecules from the carpanone-based library that inhibit exocytosis from the Golgi apparatus. The most potent member of this series has an IC50 of 14 μM. We also report structure-activity relationships for the molecules exhibiting this interesting phenotype. These inhibitors of exocytosis may be useful reagents for the study of vesicular traffic.
- Goess, Brian C.,Hannoush, Rami N.,Chan, Lawrence K.,Kirchhausen, Tomas,Shair, Matthew D.
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p. 5391 - 5403
(2007/10/03)
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- Study on the synthesis and cytotoxicity of new quinophenoxazine derivatives
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We have synthesized several new quinophenoxazine analogues and tested their cytotoxicity activities. The results showed that the compounds, 4a and 4b, possessing phenyl ring in the structure have almost same pharmacological capacity with A-62176. This finding suggests that the phenyl ring portion is important to this series of compounds for the activity expression.
- Kwon, Youngjoo,Na, Younghwa
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p. 248 - 251
(2007/10/03)
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- 2-Arylallyl as a new protecting group for amines, amides and alcohols
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Amines, amides and ethers containing 2-arylallyl groups are selectively and easily deprotected with tert-butyllithium. This transformation probably involves a carbolithiation reaction of the styrenyl moiety followed by a β-elimination process. The Royal Society of Chemistry 2005.
- Barluenga, Jose,Fananas, Francisco J.,Sanz, Roberto,Marcos, Cesar,Ignacio, Jose M.
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p. 933 - 935
(2007/10/03)
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- Selectivity adjustment in the cleavage of allyl phenyl and methyl phenyl ethers with boron trifluoride-methyl sulfide complex
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Cleavage of model allyl phenyl and methyl phenyl ethers with boron trifluoride-methyl sulfide complex is described. The demonstrated strong dependence of the reaction rate on the substitution pattern of the phenyl ring and the reaction conditions make it potentially possible to selectively cleave a single methoxy (or allyloxy) group in poly methoxy (or allyloxy) compounds. Georg Thieme Verlag Stuttgart.
- Konieczny, Marek T.,Maciejewski, Grzegorz,Konieczny, Wojciech
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p. 1575 - 1577
(2007/10/03)
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- Antidiabetic activity of passive nonsteroidal glucocorticoid receptor modulators
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Much has been learned about the consequences of glucocorticoid receptor antagonism by studying steroidal active antagonists such as RU-38486 (1). In the liver glucocorticoid receptor antagonism suppresses hepatic glucose production decreasing plasma glucose levels; however, extrahepatic antagonism produces several undesirable side effects including activation of the hypothalamic pituitary adrenal axis. A series of nonsteroidal passive N-(3-dibenzylamino-2- alkyl-phenyl)-methanesulfonamide glucocorticoid receptor modulators was discovered. Liver selective and systemically available members of this series were found and characterized in diabetes and side effect rodent models. A highly liver selective member of this series, acid 14, shows efficacy in the ob/ob model of diabetes. It lowers plasma glucose, cholesterol, and free fatty acid concentrations and reduces the rate of body weight gain. The structurally related systemically available passive modulator 12 lowers glucose, HbA 1c, triglyceride, free fatty acid, and cholesterol levels. Interestingly, it did not acutely activate the hypothalamic pituitary adrenal axis in unstressed CD-1 mice or have the abortive effects observed with 1. These results indicate that passive GR antagonists may have utility as antidiabetic agents.
- Link,Sorensen, Bryan,Patel, Jyoti,Grynfarb, Marlena,Goos-Nilsson, Annika,Wang, Jiahong,Fung, Steven,Wilcox, Denise,Zinker, Brad,Nguyen, Phong,Hickman, Bach,Schmidt, James M.,Swanson, Sue,Tian, Zhenping,Reisch, Thomas J.,Rotert, Gary,Du, Jia,Lane, Benjamin,Von Geldern, Thomas W.,Jacobson, Peer B.
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p. 5295 - 5304
(2007/10/03)
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- Zinc-catalyzed Williamson ether synthesis in the absence of base
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A zinc-catalyzed Williamson ether synthesis is described with microwave heating in the presence of DMF or stirring in an oil-bath using THF as solvent and in the absence of base. Zinc powder was found to be a highly efficient catalyst for the synthesis of aromatic ethers using microwave heating in the presence of N,N-dimethylformamide as well as under stirring in an oil-bath using tetrahydrofuran as solvent without any inorganic base. This method can be used for selective mono-, di- or tri-O-alkylations.
- Paul, Satya,Gupta, Monika
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p. 8825 - 8829
(2007/10/03)
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- Allylation of Alcohols and Carboxylic Acids with Allyl Acetate Catalyzed by [Ir(cod)2]+BF4- Complex
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A facile method for the synthesis of allyl alkyl ethers from alcohols with allyl acetate was developed by the use of [Ir(cod)2] +BF4- complex. For instance, the reaction of allyl acetate with n-octyl alcohol in the presence of a catalytic amount of [Ir(cod)2]+BF4- complex afforded allyl octyl ether in quantitative yield. Allyl carboxylates were also prepared by the exchange reaction between carboxylic acids and allyl acetate in good yields. The [Ir(cod)2]+BF4- complex catalyzed the reaction of alkyl and aromatic amines with allyl acetate to lead to the corresponding allylamines in fair to good yields.
- Nakagawa, Hideto,Hirabayashi, Tomotaka,Sakaguchi, Satoshi,Ishii, Yasutaka
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p. 3474 - 3477
(2007/10/03)
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- Development of a catalytic electron transfer system mediated by transition metal ate complexes: Applicability and tunability of electron-releasing potential for organic transformations
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We have developed a catalytic electron transfer (ET) system composed of a transition metal ate complex (Me3M(II)Li; M = Co(II), Mn(II), Fe(II)) and magnesium. This system (catalytic Me3M(II)Li/Mg) turned out to be effective for various ET reactions, such as the desulfonylation of N-phenylsulfonyl amides, and others (the chemoselective cleavage of O-allyl groups, the reduction of nitro groups, the partial reduction of diketones, and the reductive coupling of diphenyliodonium salt). The ET ability of this system can be tuned by changing the ligands of the ate complexes. This tunability was experimentally and electrochemically demonstrated: alkoxy-ligated and dianion-type ET ate complexes showed attenuated and enhanced reducing abilities, respectively. The modification of the ET abilities was evaluated by means of electrochemical measurements and chemical reactions. These results provide a basis for the design of various tailor-made ET ate complexes.
- Uchiyama, Masanobu,Matsumoto, Yotaro,Nakamura, Shinji,Ohwada, Tomohiko,Kobayashi, Nagao,Yamashita, Natsuno,Matsumiya, Atsushi,Sakamoto, Takao
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p. 8755 - 8759
(2007/10/03)
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- Synthesis, activity, metabolic stability, and pharmacokinetics of glucocorticoid receptor modulator-statin hybrids
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The synthesis, activity, metabolic stability, and pharmacokinetics of steroidal and nonsteroidal glucocorticoid receptor modulator-statin hybrids is reported. Potent steroidal antagonist-statin hybrids like 22 (h-GR binding IC50=7nM) and nonsteroidal modulator hybrids like 16 (h-GR binding IC50=2nM) were discovered. Appending a 'statin'-like diol-acid group to the modulators dramatically improved metabolic stability (and in some cases hepatocyte activity), but did not impart hepatoselectivity.
- Link,Sorensen, Bryan K.,Lai, Chunqiu,Wang, Jiahong,Fung, Steven,Deng, Daisy,Emery, Maurice,Carroll, Sherry,Grynfarb, Marlena,Goos-Nilsson, Annika,Von Geldern, Thomas
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p. 4173 - 4178
(2007/10/03)
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- One step hair coloring compositions using salts
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A hair coloring composition comprising the following two compositions which are mixed just prior to application to the hair: (a) a composition comprising a water-soluble peroxygen oxidizing agent; and (b) a composition comprising one or more oxidative hair coloring agents selected from the group consisting of an aromatic diamine, an amino phenol, a naphthol, a polyhydric phenol, a catechol and mixtures thereof; wherein the composition comprising one or more oxidative hair coloring agents further comprises al least one water soluble carbonate releasing salts; and optionally a water soluble ammonium salt, is described.
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- Synthesis and binding affinities of fluoroalkylated raloxifenes
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Three fluoroalkylated derivatives (1-3) of the selective estrogen receptor modulator (SERM), raloxifene, have been synthesized. The key step in the synthesis is the C-C bond formation of benzo[b]thiophene and a substituted phenyl group (ring C) using a Stille reaction. The in vitro binding affinities of the substituted raloxifenes 1-3 are 45, 60, 89%, respectively, relative to the affinity of estradiol, which is higher than the affinity of raloxifene itself (25%). When labeled with the positron-emitting radionuclide, these compounds might be useful as PET imaging agents for estrogen receptor-positive breast tumors.
- Lee, Kyo Chul,Moon, Byung Seok,Lee, Jae Hak,Chung, Kyoo-Hyun,Katzenellenbogen, John A.,Chi, Dae Yoon
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p. 3649 - 3658
(2007/10/03)
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- Efficient, selective deprotection of aromatic acetates catalyzed by Amberlyst-15 or iodine
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Aromatic acetates were selectively deprotected in the presence of aliphatic acetates to the corresponding phenols in excellent yields using Amberlyst-15 or iodine as catalysts in methanol at room temperature. The first catalyst can be recovered.
- Das, Biswanath,Banerjee, Joydeep,Ramu,Pal, Rammohan,Ravindranath,Ramesh
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p. 5465 - 5468
(2007/10/03)
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- Transition metal complexes as dye forming catalysts in hair coloring compositions
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A hair coloring composition comprising a first composition which comprises: (a) a dye forming transition metal salt or complex; which is first applied to the hair; and a second composition which comprises the following two compositions which are mixed just prior to application to the hair: (a) a composition comprising a water-soluble peroxygen oxidizing agent; and (b) a composition comprising one or more oxidative hair coloring agents selected from the group consisting of an aromatic diamine, an aminophenol, a polyhydric phenol a catechol and mixtures thereof.
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- Enhanced color deposition for hair with sequestering agents
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Hair coloring compositions which comprise: (A) non-nitrogenous chelating agents from the group consisting of polyphosphate; phosphonates; hydroxycarboxylates; polyacrylates; zeolite; and mixtures thereof; (B) an oxidative dye primary intermediate; and (C) an oxidative dye coupler; (D) and water are described. The present invention also relates to a method for coloring hair which comprises contacting said hair with a hair coloring composition as described above.
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- Novel synthesis of monoethers of hydroquinone and resorcinol on soluble polymer-supports
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Monoethers of hydroquinone and resorcinol were easily prepared using PEG as soluble polymer-supports, monoprotection group and phase transfer catalyst with good yields and high selectivity of functionlization in homogenous solution.
- Yang, Guichun,Chen, Zuxing,Zhang, Zhaojun,Qiu, Xiaoling
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p. 3637 - 3642
(2007/10/03)
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- GLUCOCORTICOID RECEPTOR MODULATORS
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Compounds of formula (I) or pharmaceutically acceptable salts thereof are novel glucocorticoid receptor modulators and are useful for treating type II diabetes in a mammal.
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- Arylthiazolidinedione and aryloxazolidinedione derivatives
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Substituted 5-aryl-2,4-thiazolidinediones or 5-aryl-2,4-oxazolidinediones that also carry a second substituent in the 5-position of the heterocyclic ring are potent agonists of PPAR, and are therefore useful in the treatment, control or prevention of diabetes, hyperglycemia, hyperlipidemia (including hypercholesterolemia and hypertriglyceridemia), atherosclerosis, obesity, vascular restenosis, and other PPAR α, δ and/or γ mediated diseases, disorders and conditions.
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- Synthesis of functionalized long-chain thiols and thiophenols for the formation of self-assembled monolayers on gold
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The terminally 2-thienyl- and phenyl-substituted eicosane derivatives 4 and 5 were prepared by reacting 1-[(20-bromoeicosyl)oxy]-4-methoxybenzene (3) with 2-lithiothiophene and lithium diphenylcuprate, respectively. Reaction of 4 and 5 with BBr3 leads to the corresponding bromides 6, 7 which afforded the aryl-substituted eicosanethiols 8 and 9 by nucleophilic substitution with thiourea. 4-Eicosylthiophenol (13) was prepared from eicosylbenzene (11) by chlorosulfonation and subsequent reduction of the sulfonyl chloride. Synthesis of the thiol 22 with phenylenedioxy groups incorporated in the alkyl chain involves formation of 19 from allyloxy(bromobutoxy)benzene (18) and (4-(2-thienyl)butoxy)phenol (17). Hydroboration of 19 yields the corresponding alcohol 20, which under Mitsunobu conditions and subsequent reduction with LiAlH4 can be transformed to 22.
- Buckel, Frank,Persson, Per,Effenberger, Franz
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p. 953 - 958
(2007/10/03)
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- Arylthiazolidinedione derivatives
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Substituted 5-aryl-2,4-thiazolidinediones are potent agonists of PPAR, and are therefore useful in the treatment, control or prevention of diabetes, hyperglycemia, hyperlipidemia (including hypercholesterolemia and hypertriglyceridemia), atherosclerosis, obesity, vascular restenosis, and other PPAR α, δ and/or γ mediated diseases, disorders and conditions.
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- Liquid Crystalline Asymmetric Bisphenyl-4,4'-bibenzyldicarboxylates and Polysiloxanes with Bisphenyl-4,4'-bibenzyldicarboxylat Components in the Side Chains, Synthesis and Characterization
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Asymmetric bisphenyl bibenzyl-4,4'-dicarboxylates with an alkenyloxy- or the 10-undecenoylgroup in the p-position of one terminal benzene ring and the butyl-, an alkoxy- or the thiomethylgroup in the p-position of the other terminal benzene ring (12-14) are synthesized.The olefins 12-14 are added to a poly(methylhydrogensiloxane) 15 to give mesomorphic side chain polysiloxanes 16-18.Data of liquid crystalline properties of 12-14, 16-18 and precursors are discussed.
- Boberg, Friedrich,Mueller, Enno,Reddig, Wolfram
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p. 136 - 142
(2007/10/02)
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- Allylation of Quinones via Photoinduced Electron-Transfer Reactions from Allylstannanes
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Photochemical reactions of quinones with allylstannanes provided four types of products: adducts of allyl group to the carbonyl oxygens of quinones, adducts of allyl group to the olefinic carbons, adducts of allyl group to the carbonyl carbons, and hydroquinones.An electron-transfer mechanism was confirmed by 1H-CIDNP (Chemically Induced Dynamic Nuclear Polarization) method.This study suggests that a) photoinduced electron transfer from allylstannanes to quinones produces the corresponding quinone anion radicals and tin cation radicals, b) the tin cation radicals cleave to give allyl radicals as well as tin cation, and c) the allyl radicals attack the quinone anion radicals resulting in the formation of final products, allylated quinones.
- Maruyama, Kazuhiro,Imahori, Hiroshi
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p. 816 - 825
(2007/10/02)
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- Syntheses of Sulfinylmethyl Ethers and Conversion of these into Halomethyl and Acyloxymethyl Ethers
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Halomethyl ethers can be prepared from sulfinyl ethers by cleavage of the carbon-sulfur bond with thionyl chloride, acetyl chloride or trimethylsilyl halides.In the presence of alkenyl groups in the substrate, acetyl chloride is the reagent of choice.Trifluoroacetic anhydride reacts in the same manner to form the trifluoroacetoxymethyl ether.With acetic anhydride, catalysis by methanesulfonic acid was required.At elevated temperatures in the presence of sodium acetate the products were formed by the Pummerer rearrangement.
- Antonsen, Oeyvind,Benneche, Tore,Undheim, Kjell
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p. 515 - 523
(2007/10/02)
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- Preparation of monoalkylated dihydroxybenzenes
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Preparation of monoethers of dihydroxybenzenes from an alkenylphenol and an alkylating agent and thereafter oxidizing in the presence of an acid catalyst.
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- 2-Ethoxyethyl 2-(4-hydroxyphenoxy)-propanoate
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Preparation of monoethers of dihydroxybenzenes from an isopropenylphenol and an alkylating agent and thereafter oxidizing in the presence of an acid catalyst.
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- Enzyme-activated oxidative process for coloring hair
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An enzyme-based oxidative process for coloring hair wherein the hair is exposed to a solution having a pH of about 4 to about 10 and containing hydrogen peroxide, soybean peroxidase enzyme and one or more oxidation dye precursors.
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