- Mechano- and Thermo-responsive Luminescence of Crystalline Thienylbenzothiadiazole Derivatives: Stepwise Hypsochromic Switching of Near-Infrared Emission
-
Organic crystals that exhibit mechanochromic luminescence (MCL) switch their emission colors in response to mechanical stimuli, and the original emission colors usually recover upon heating the mechanically changed state. Contrary to the recent enthusiastic investigations of MCL crystals, only a limited number of organic crystals transform to another state showing a third emission color upon sequential exposure to mechanical and thermal stimuli. The development of near-infrared (NIR) emissive organic crystals is another challenge. Although several NIR-emissive crystals that can respond to mechanical stimuli have been developed, further investigations are still required for the multi-stimuli-responsive emission involving the NIR region. In this study, we investigate the mechano-responsive properties of crystalline thienylbenzothiadiazole derivatives. The maximum emission wavelengths of these crystals are observed between blue-green to NIR (502–731 nm), which depend on the substituents R1 and R2 on the thiophene and benzothiadiazole rings, respectively. All derivatives shift the emission wavelength in the hypsochromic direction upon grinding. Moreover, derivatives having a carbonyl group on R2 display further hypsochromic shifts of their emission bands by thermal annealing of the ground states. Specifically, a stepwise hypsochromic shift of the emission from the NIR region has been achieved for a derivative bearing phenyl and formyl groups (R1 = Ph, R2 = CHO). Powder X-ray diffraction analysis, differential scanning calorimetry, and spatially resolved fluorescence microscopy have suggested that the stepwise emission-color switching should be attributed to the crystal-size-dependent luminescence of the carbonyl-substituted derivatives. The present study can be expected to provide useful insights into developing diverse multi-stimuli-responsive luminescent organic crystals and thus accelerate the practical applications of luminescent sensor systems.
- Ito, Suguru,Tachikawa, Takashi,Yoshida, Ryohei
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p. 547 - 558
(2022/01/03)
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- Virtues of Volatility: A Facile Transesterification Approach to Boronic Acids
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Boronic acids are an increasingly important compound class for many applications, including C-C bond formation reactions, medicinal chemistry, and diagnostics. The deprotection of boronic ester intermediates is frequently a problematic and inefficient step in boronic acid syntheses. We describe an approach that highly facilitates this transformation by leveraging the volatility of methylboronic acid and its diol esters. The method is performed under mild conditions, provides high yields, and eliminates cumbersome and problematic purification steps.
- Hinkes, Stefan P.A.,Klein, Christian D.P.
-
supporting information
p. 3048 - 3052
(2019/05/10)
-
- Ligand-Less Iron-Catalyzed Aromatic Cross-Coupling Difluoromethylation of Grignard Reagents with Difluoroiodomethane
-
Iron-catalyzed cross-coupling difluoromethylations of the Grignard reagents with difluoroiodomethane provide various aromatic difluoromethyl products in good yields, not employing sterically demanding ligands. Difluoromethylations proceed within 30 min at -20 °C with 2.0 equiv of the Grignard reagents and FeCl3 or Fe(acac)3 (2.5 mol %). Mechanistic investigations clarify difluoromethyl radical intervention; Fe(0) ate is initially generated. Single-electron transfer from Fe(0) ate to difluoroiodomethane takes place. Recombination with aryl groups gives Ar-CF2Hs. The catalyst can be regenerated by the Grignard reagents.
- Motohashi, Hirotaka,Kato, Miki,Mikami, Koichi
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p. 6483 - 6490
(2019/05/16)
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- Magnesium promoted autocatalytic dehydrogenation of amine borane complexes: A reliable, non-cryogenic, scalable access to boronic acids
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Owing to the unusual reactivity of dialkylamine-borane complexes, a methodology was developed to simply access boronic acids. The intrinsic instability of magnesium aminoborohydride was tweaked into a tandem dehydrogenation borylation sequence. Proceeding via an autocatalytic cycle, amineborane dehydrogenation was induced by a variety of Grignard reagents. Overall, addition of the organomagnesium species onto specially designed dialkylamine-borane complexes led to a variety of boronic acids in high yields. In addition, the reaction can be performed under Barbier conditions, on a large scale.
- Marciasini, Ludovic D.,Richard, Jimmy,Cacciuttolo, Bastien,Sartori, Guillaume,Birepinte, Melodie,Chabaud, Laurent,Pinet, Sandra,Pucheault, Mathieu
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p. 164 - 171
(2018/12/05)
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- THERANOSTIC AGENTS
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A theranostic agent can be used in both photoacoustic imaging (PAI) and photothermal therapy (PTT) applications. The theranostic agent can include a small molecule, organic compound with absorption in the near-infrared (NIR) interrogation window (700-900 nm). The compound can be a biocompatible organic nanoparticle (ONP). The theranostic agent can be effectively used in PAI and PAI-guided PTT applications. The theranostic agent can be administered to a patient to locate a tumor site in the patient using invivo imaging techniques. Once the tumor site has been determined, the tumor site can be irradiated with near-infrared light to stop or inhibit the growth of the tumor.
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Page/Page column 26-27
(2018/12/13)
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- Evidence for Interfacial Halogen Bonding
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A homologous series of donor-π-acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye-X (X=F, Cl, Br, and I) was immobilized on a TiO2 surface to investigate how the halogen substituents affect the reaction between the light-induced charge-separated state, TiO2(e-)/Dye-X+, with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye-F Dye-Cl Dye-Br Dye-I. Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ-hole on the heavier halogens, the differences in dye regeneration kinetics for Dye-Cl, Dye-Br, and Dye-I are ascribed to the extent of halogen bonding with the nucleophilic solution species.
- Swords, Wesley B.,Simon, Sarah J.C.,Parlane, Fraser G.L.,Dean, Rebecca K.,Kellett, Cameron W.,Hu, Ke,Meyer, Gerald J.,Berlinguette, Curtis P.
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p. 5956 - 5960
(2016/05/19)
-
- Synthesis and characterization of conjugated polymers based on benzoselenadiazole
-
A multistep synthesis of the electron-poor 4,7-di(thiophen-2-yl)benzo[c][1,2,5]selenadiazole are presented. The new deficient acceptor has good solubility in organic solvents to permit an appropriate coating process. P1 was synthesized by direct oxidative polymerization under the reaction condition with FeCl3 and CH3NO2. The spectra of polymers P1 to P2 show homogenous absorptions across most of the visible spectrum (450-650 nm). Solutions of P1 show a dark purple-black colour due to the lack of absorption in the far blue and red regions. And the solution of P2 exhibits a bright orange-red colour due to the increased reflection/transmission of red light. Both of the polymers were characterized by IR, UV-visible and cyclic voltammetry.
- Sun, Xiaoxia,Lei, Xiaolong,Hu, Yu
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p. 2427 - 2430
(2015/12/11)
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- SYNTHESIS OF BORONIC ESTERS AND BORONIC ACIDS USING GRIGNARD REAGENTS
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Boronic esters and boronic acids are synthesized at ambient temperature in an ethereal solvent by the reaction of Grignard reagents with a boron-containing substrate. The boron-containing substrate may be a boronic ester such as pinacolborane, neopentylglycolborane, or a dialkylaminoborane compound such as diisopropylaminoborane. The Grignard reagents may be preformed or generated from an alkyl, alkenyl, aryl, arylalkyl, heteroaryl, vinyl, or allyl halide compound and Mg°. When the boron-containing substrate is a boronic ester, the reactions generally proceed at room temperature without added base in about 1 to 3 hours to form a boronic ester compound. When the boron-containing substrate is a dialkylaminoborane compound, the reactions generally proceed to completion at 0°C in about 1 hour to form a boronic acid compound.
- -
-
Paragraph 0114; 0117
(2013/03/26)
-
- Mn-catalyzed aromatic C-H alkenylation with terminal alkynes
-
The first manganese-catalyzed aromatic C-H alkenylation with terminal alkynes is described. The procedure features an operationally simple catalyst system containing commercially available MnBr(CO)5 and dicyclohexylamine (Cy2NH). The reaction occurs readily in a highly chemo-, regio-, and stereoselective manner delivering anti-Markovnikov E-configured olefins in high yields. Experimental study and DFT calculations reveal that (1) the reaction is initiated by a C-H activation step via the cooperation of manganese and base; (2) manganacycle and alkynylmanganese species are the key reaction intermediates; and (3) the ligand-to-ligand H-transfer and alkynyl-assisted C-H activation are the key steps rendering the reaction catalytic in manganese.
- Zhou, Bingwei,Chen, Hui,Wang, Congyang
-
supporting information
p. 1264 - 1267
(2013/03/14)
-
- Reaction of grignard reagents with diisopropylaminoborane. Synthesis of alkyl, aryl, heteroaryl and allyl boronic acids from organo(diisopropyl)- aminoborane by a simple hydrolysis
-
Diisopropylaminoborane (BH2-N(iPr)2) is prepared by reacting lithium diisopropylaminoborohydride (iPr-LAB) with trimethylsilyl chloride (TMSCl). Aliphatic, aromatic, and heteroaromatic (diisopropylamino) boranes are readily synthesiz
- Bailey, Christopher L.,Murphy, Chris L.,Clary, Jacob W.,Eagon, Scott,Gould, Naomi,Singaram, Bakthan
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p. 331 - 341
(2013/08/23)
-
- On the directing effect of boronate groups in the lithiation of boronated thiophenes
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An investigation of thiophene boronates has revealed the usefulness of a metalation reaction in the synthesis of various lithiated thiophene boronates, which were further converted to functionalized thiopheneboronic derivatives. The lithiation of 2- and 3-thienylboronic N-butyldiethanolamine (BDEA) esters with lithium diisopropylamide and lithium 2,2,6,6-tetramethylpiperidide showed that both boronated thiophenes were readily deprotonated. In the latter case, lithiation at the 2-position adjacent both to sulfur and the borocanyl group is thermodynamically favoured due to the significant stabilizing effect of the borocanyl group. Further derivatization with a range of electrophiles followed by hydrolysis afforded various 2-substituted 3-thiopheneboronic acids. Lithiation of the corresponding thiopheneboronic "ate" complexes of the type [ThB(OR)3]Li revealed that the 2-thienyl derivatives could not be effectively deprotonated, whereas the "ate" complex, [3-ThB(OEt)3]Li, was selectively lithiated with nBuLi at C-2. This points to a directing effect of the anionic boronate moiety. The resulting bimetallic species, [(2-Li-3-Th)B(OEt)3]Li, underwent ring-closing dimerization upon heating to give, after subsequent hydrolysis, 4,8-dihydro-4,8-dihydroxy-p-diborino[2,3-b:5,6-b′]dithiophene - a cyclic diborinic acid. A computational study of the lithiation of boronated thiophenes and furans proved that boronation decreases ring-proton acidity. This effect is much stronger for the boronic "ate" complexes than for the corresponding neutral BDEA esters. Calculations of the transition states have shown that the specific directing effect of boronate groups in 3-thienyl derivatives is due to intramolecular oxygen-lithium coordination.
- Borowska, Elena,Durka, Krzysztof,Lulinski, Sergiusz,Serwatowski, Janusz,Wozniak, Krzysztof
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scheme or table
p. 2208 - 2218
(2012/06/01)
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- Palladium-catalyzed borylation of aryl and heteroaryl halides utilizing tetrakis(dimethylamino)diboron: One step greener
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The palladium-catalyzed borylation of aryl and heteroaryl halides with a novel borylating agent, tetrakis(dimethylamino)diboron [(Me2N) 2B-B(NMe2)2], is reported. The method is complementary to the previously reported method utilizing bis-boronic acid (BBA) in that certain substrates perform better under one set of optimized reaction conditions than the other. Because tetrakis(dimethylamino)diboron is the synthetic precursor to both BBA and bis(pinacolato)diboron (B 2Pin2), the new method represents a more atom-economical and efficient approach to current borylation methods.
- Molander, Gary A.,Trice, Sarah L. J.,Kennedy, Steven M.
-
supporting information
p. 4814 - 4817,4
(2012/12/12)
-
- Synthesis and characterization of planar five-ring-fused dithiophene-dione
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A series of new organic semiconductors based on s-indaceno[1,2-b:5,6- b′]dithiophene-4,9-dione was successfully synthesized and characterized. The electron withdrawing carbonyl group lowers the LUMO energy levels, leading to increased electronegativities, which is beneficial for high photo-stability in air. The n-alkyl substituted compounds, 1c and 1d, crystallize with the rigid coplanar systems packed into slipped face-to-face π-stacks. Interestingly, 1c and 1d also show liquid crystalline behaviors, which give highly ordered molecular packing over large area.
- Wang, Jing,Zeng, Weijing,Xu, Huan,Li, Bin,Cao, Xiaoping,Zhang, Haoli
-
experimental part
p. 681 - 688
(2012/06/04)
-
- Synthetic routes to fluorescent dyes exhibiting large stokes shifts
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Derivatives of isomeric 2-(hydroxytolyl)-4,6-dimethylamino-1,3,5-triazines have been synthesized in high yields in a controlled manner using a multistep reaction sequence. Iodination of either 2-(1′-hydroxy-6′-methylphen- 2′-yl)- or 2-(1′-hydroxy-4′-methylphen-2′-yl)-4,6- dimethylamino-1,3,5-triazine with ICl provides species differing in the positioning of the iodo group relative to the hydroxyl which readily undergo Suzuki, Sonogashira, and Heck reactions under Pd(0) catalysis. Thus, thienyl, bisthienyl, and 3,4-ethylenedioxythienyl groups have been directly grafted, while unsubstituted polycyclic aromatics such as pyrene and perylene have been linked via alkyne bridges, as have ethynyldifluoroborondipyrromethane (BODIPY) dyes prepared in situ. The presence of a hydrogen bond in the ground state involving the hydroxyl substituent has been established by proton NMR and several X-ray structure determinations. All of the new dyes with a simple substituent (phenyl, thienyl) exhibited a pronounced green fluorescence resulting from an intramolecular proton transfer in the excited state (ESIPT) which produces a large Stokes shift (>10 000 cm-1). With other dyes, the fluorescence of the keto form responsible for the ESIPT process could be used as the input energy in efficient intramolecular energy transfer processes. Replacing perylene with pyrene allowed reversal of the direction of energy transfer from the polyaromatic module to the keto form.
- Rihn, Sandra,Retailleau, Pascal,De Nicola, Antoinette,Ulrich, Gilles,Ziessel, Raymond
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p. 8851 - 8863
(2013/01/15)
-
- Lithium aminoborohydrides 17. Palladium catalyzed borylation of aryl iodides, bromides, and triflates with diisopropylaminoborane prepared from lithium diisopropylaminoborohydride
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The Alcaraz-Vaultier borylation of aryl halides and triflates is reported utilizing diisopropylaminoborane (BH2N(iPr)2) prepared from the corresponding lithium aminoborohydride (LAB reagent). BH 2N(iPr)2, prepared by reacting lithium diisopropylaminoborohydride with trimethylsilyl chloride, provided the most consistent isolated yields from this reaction. Catalytic amounts of palladium dichloride produced the highest yields from aryl iodides, while catalytic tris(dibenzylideneacetone)dipalladium(chloroform) provided the best yields for aryl bromides and triflates. This route to boronic acids is mild enough to tolerate various functionalities and for the first time employs aryl triflates as substrates for the Alcaraz-Vaultier borylation. In addition, it was found that both boronic acid and ester compounds could be isolated from the reaction mixture utilizing simple work-up procedures. Treatment of the reaction intermediate with an acid/base work-up provided the corresponding boronic acid, while treating the same intermediate with a diol, such as neopentyl glycol, afforded the corresponding boronic ester.
- Haddenham, Dustin,Bailey, Christopher L.,Vu, Chau,Nepomuceno, Gabby,Eagon, Scott,Pasumansky, Lubov,Singaram, Bakthan
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experimental part
p. 576 - 583
(2011/03/18)
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- SLOW RELEASE OF ORGANOBORONIC ACIDS IN CROSS-COUPLING REACTIONS
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A method of performing a chemical reaction includes reacting a compound selected from the group consisting of an organohalide and an organo-pseudohalide, and a protected organoboronic acid represented by formula (I) in a reaction mixture: R1-B-T; where R1 represents an organic group, T represents a conformationalIy rigid protecting group, and B represents boron having sp3 hybridization. When unprotected, the corresponding organoboronic acid is unstable by the boronic acid neat stability test. The reaction mixture further includes a base having a pKB of at least 1 and a pal ladium catalyst. The method further includes forming a cross-coupled product in the reaction mixture.
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Page/Page column 41, 42
(2010/04/27)
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- PERYLENE TETRACARBOXIMIDE DERIVATIVES FOR PHOTOVOLTAIC DEVICES
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The compounds of the present invention are represented by the following formula (I): wherein M is represented by the following formula: with R1, R2, R3, R4, R5, R6, R7, R8, R10, R11, X1, X2, X3, L, a, b, c, d, e, x, y, and z defined herein.
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Page/Page column 22
(2010/04/03)
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- Synthesis, photophysics, and electrochemistry of thiophene-pyridine and thiophene-pyrimidine dyad comonomers
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A series of new π-conjugated donor (D) and acceptor (A) dyad comonomers were prepared using Suzuki coupling protocols. The D-A comonomers consisting of thiophene/bithiophene as donors and pyridine/pyrimidine as acceptors were prepared to investigate their photophysical and electrochemical properties. The dyads were spectroscopically confirmed to be highly conjugated. This was further supported by the X-ray crystal structure of the bithophene-pyridine dyad that showed all the heterocycles to be coplanar. It was further found that the fluorescence yields (Φfl) of die dyads were highly dependent on the number of thiophenes. The bithiophene derivatives exhibited Φfl values ≥ 0.3 while die thiophene derivatives did not fluoresce. The suppressed fluorescence observed for me thiophene derivatives was due to tiieir higher triplet energy resulting in efficient intersystem crossing (ISC) to the triplet state with ΦISC ≥ 0.8. This was confirmed both by time-resolved and steady-state measurements. The singlet excited state of both thiophene and bithiophene dyads was deactivated solely by either fluorescence and (or) ISC. Owing to their donor and acceptor character, die dyads could be oxidized and reduced both electrochemically and photochemically to afford the radical cation and anion, respectively.
- Bolduc, Andreanne,Dufresne, Stephane,Hanan, Garry S.,Skene
-
experimental part
p. 236 - 246
(2010/06/17)
-
- Efficient hydrolysis of organotrifluoroborates via silica gel and water
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(Chemical Equation Presented) A general, mild, and efficient method for the hydrolysis of organotrifluoroborates to unveil boronic acids using silica gel and H2O was developed. This method proved to be tolerant of a broad range of aryl-, heteroaryl-, alkenyl-, and alkyltrifluoroborates as well as structurally diverse aminomethylated organotrifluoroborates.As anticipated, electron-rich substrates provided the corresponding boronic acids more readily than electron-poor substrates, owing to the resonance-stabilized difluoroborane intermediate. The method developed was expanded further for the conversion of organotrifluoroborates to the corresponding boronate esters. 2009 American Chemical Society.
- Molander, Gary A.,Cavalcanti, Livia N.,Canturk, Belgin,Pan, Po-Shen,Kennedy, Lauren E.
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supporting information; experimental part
p. 7364 - 7369
(2010/01/16)
-
- A series of red-light-emitting ionic iridium complexes: Structures, excited state properties, and application in electroluminescent devices
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A series of ionic diiminoiridium complexes [Ir(piq-C∧N) 2(L-N∧N)](PF6) were prepared, where piq-C∧N is 1-phenylisoquinolinato and L-N∧N are bidentate N-coordinating ligands: 2,2′-bipyridine (bpy), 4,4′-dimethyl-2,2′-bipyridine (mbpym), 5,5′-bis(thiopen-2-yl)-2,2′-bipyridine (tbpyt), and 5,5′-bis(9,9-dioctylfluoren-2-yl)-2,2′-bipyridine (FbpyF). X-ray diffraction studies of [Ir(piq)2(mbpym)](PF6) revealed that the iridium center adopts a distorted octahedral geometry. All complexes exhibited intense and long-lived emission at room temperature. The substituents on the 2,2′-bipyridine moieties influence the photophysical and electrochemical properties. The excited states were investigated through theoretical calculations together with photophysical and electrochemical properties. It was found that the excited state of the [Ir(piq) 2(FbpyF)](PF6) complex can be assigned to a mixed character of 3LC (πN∧N→π *N∧N), 3MLCT, 3LLCT (π C∧N→π*N∧N), and 3LC (πC∧N→π*C∧N). In addition, the alkylfluorene-substituted complex, [Ir(piq)2(FbpyF)](PF6), had relatively high quantum efficiency and good film-forming ability, and it was expected to be a good candidate for lighting and display applications. A nondoped, single-layer device that incorporates this complex as a light-emitting layer was fabricated and red phosphorescence was obtained. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Liu, Shu-Juan,Zhao, Qiang,Fan, Qu-Li,Huang, Wei
-
experimental part
p. 2177 - 2185
(2009/02/07)
-
- Fluorescence "turn-on" sensing of carboxylate anions with oligothiophene-based o-(carboxamido)trifluoroacetophenones
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(Chemical Equation Presented) o-(Carboxamido)trifluoroacetophenones containing ter- or pentathiophene moiety as a fluorophore exhibit fluorescence enhancement upon binding carboxylate anions. Particularly, the terthiophene derivative shows a large fluorescence enhancement factor (FEF = 120). The enhancement is explained by intramolecular H-bonding stabilization of an anion-ionophore adduct, through which a possible quenching process, the n-π* transition from the trifluoroacetophenone moiety, is eliminated.
- Kim, Dae-Sik,Kyo, Han Ahn
-
p. 6831 - 6834
(2008/12/22)
-
- Preparation, photophysics, and electrochemistry of segmented comonomers consisting of thiophene and pyrimidine units: New monomers for hybrid copolymers
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An efficient coupling route to novel π-conjugated comonomers consisting of pyrimidine, thiophene, and bithiophene units was developed. The novel π-donor-acceptor-donor and π-donor-acceptor-acceptor-donor conjugated compounds were prepared by Suzuki heterocoupling and Ni(0)-mediated Ullman homocoupling reactions. Photophysical investigation of these alternating π-donor and acceptor compounds indicated that the deactivation of their singlet excited State proceeds predominately by fluorescence and results in high fluorescence quantum yields. Intersystem crossing to the triplet state was also present in ca. 10%. Quantification of the triplet manifold by laser flash photolysis further revealed that bithiophene ,produced its triplet state in only 31%. Cyclic voltammetry studies showed that the comonomers undergo both oxidation and reduction leading to their radical cations and radical anions, respectively. The radical cations are highly reactive and undergo anodic polymerization resulting in mutual p- and n-type dopable polymers. The extended conjugation resulting from polymer formation was confirmed by both absorbance and fluorescence spectroscopy and by GPC. Ruthenium binding with the conjugated homocoupled ligand was also found resulting in a hybrid alternating copolymer with significantly different spectroscopic and electrochemical properties relative to its metal-free counterpart.
- Dufresne, Stephane,Hanan, Garry S.,Skene
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p. 11407 - 11418
(2008/10/09)
-
- Toward Functionalized Conducting Polymers: Synthesis and Characterization of Novel β-(Styryl)terthiophenes
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Metal-catalyzed coupling methodologies have been employed in the synthesis of the key building block 3′-formyl-2,2′:5′,2″ -terthiophene. Wittig olefinations with this aldehyde have produced five novel β-styryl-substituted terthiophene monomers. These materials have been fully characterized by NMR spectroscopy, microanalysis, mass spectrometry, and X-ray crystal structure analysis. The results from the UV/visible spectroscopy and cyclic voltammetric investigations are reported.
- Collis, Gavin E.,Burrell, Anthony K.,Scott, Sonya M.,Officer, David L.
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p. 8974 - 8983
(2007/10/03)
-
- Novel synthesis of arylboronic acids by electroreduction of aromatic halides in the presence of trialkyl borates
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A novel preparation of aryl and heteroarylboronic acids by an electrochemical coupling reaction is described. It is based on the reductive coupling between aromatic or heteroaromatic halides and a trialkyl borate. The reactions are carried out in DMF or THF with the use of sacrificial aluminium or magnesium anodes in a single-compartment cell. Arylboronic acids are obtained with moderate to good selectivities and isolated yields.
- Laza, Carine,Dunach, Elisabet,Serein-Spirau, Francoise,Moreau, Joel J. E.,Vellutini, Luc
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p. 373 - 375
(2007/10/03)
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- QUINUCLIDINE DERIVATIVES AS SQUALENE SYNTHASE INHIBITORS
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Compounds of formula (I) in which R is hydrogen or hydroxy; R is hydrogen; or R and R are joined together so that CR-CR is a double bond; Ar is a phenylene moiety and Ar is a heterocyclic moiety; or Ar is a heterocyclic moiety and Ar is a phenyl moiety; and wherein one or both of Ar and Ar may optionally bear one or more substituents independently selected from halogeno, hydroxy, amino, nitro, cyano, carboxy, carbamoyl, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-6C)alkylamino, di-[(1-6C)alkyl]amino N-(1-6C)alkylcarbamoyl, di-N,N-[(1-6C)alkyl]carbamoyl, (1-6C)alkoxycarbonyl, (1-6C)alkylthio, (1-6C)alkylsulphinyl, (1-6C)alkylsulphonyl, halogeno (1-6C)alkyl, (1-6C)alkanoylamino, ureido, N'-(1-6C)alkylureido, (1-6C)alkanoyl and oxime derivatives thereof and O-(1-6C)alkyl ethers of said oxime derivatives; provided that Ar is not a 6-membered heteroaryl moiety containing one or two nitrogen atoms; when Ar and Ar are both hydrogen, Ar is not an oxadiazole moiety; and their pharmaceutically acceptable salts are inhibitors of squalene synthase and hence useful in treating medical conditions in which a lowering of cholesterol is beneficial. Processes preparing these derivatives, pharmaceutical compositions containing them are also described together with their use in medicine.
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- Substituted sulfonic acid N-[(aminoiminomethyl)phenylalkyl]-azaheterocyclylamide compounds
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The compounds of formula I exhibit useful pharmacological activity and accordingly are incorporated into pharmaceutical compositions and used in the treatment of patients suffering from certain medical disorders. More specifically, they are inhibitors of the activity of Factor Xa. The present invention is directed to compounds of formula I, compositions containing compounds of formula I, and their use, which are for treating a patient suffering from, or subject to, physiological condition which can be ameliorated by the administration of an inhibitor of the activity of Factor Xa.
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-
- Probing the hydrophobic pocket of farnesyltransferase: Aromatic substitution of CAAX peptidomimetics leads to highly potent inhibitors
-
Cysteine farnesylation at the carboxylate terminal tetrapeptide CAAX of Ras protein is catalyzed by farnesyltransferase. This lipid modification is necessary for regulatory function of both normal and oncogenic Ras. The high frequency of Ras mutation in human cancers has prompted an intensive study on finding ways of controlling oncogenic Ras function. Inhibition of farnesyltransferase is among the most sought after targets for cancer chemotherapy. We report here the design, synthesis and biological characterization of a series of peptidomimetics as farnesyltransferase inhibitors. These compounds are extremely potent towards farnesyltransferase with IC50 values ranging from subnanomolar to low nanomolar concentrations. They have a high selectivity for farnesyltransferase over the closely related geranylgeranyltransferase-I. Structure-activity relationship studies demonstrated that a properly positioned hydrophobic group significantly enhanced inhibition potency, reflecting an improved complementarity to the large hydrophobic pocket in the CAAX binding site. Copyright (C) 1999 Elsevier Science Ltd.
- Qian, Yimin,Marugan, Juan Jose,Fossum, Renae D.,Vogt, Andreas,Sebti, Said M.,Hamilton, Andrew D.
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p. 3011 - 3024
(2007/10/03)
-
- SUBSTITUTED SULFONIC ACID N-[(AMINOIMINOMETHYL)PHENYLALKYL]-AZAHETEROCYCLAMIDE COMPOUNDS
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The compounds of formula I exhibit useful pharmacological activity and accordingly are incorporated into pharmaceutical compositions and used in the treatment of patients suffering from certain medical disorders. More specifically, they are inhibitors of the activity of Factor Xa. The present invention is directed to compounds of formula I, compositions containing compounds of formula I, and their use, which are for treating a patient suffering from, or subject to, physiological condition which can be ameliorated by the administration of an inhibitor of the activity of Factor Xa.
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- SYNTHESIS OF ARYLBORONIC ACIDS VIA THE REACTION OF BORANE WITH ARYLMAGNESIUM HALIDES
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The reaction of borane complexes with arylmagnesium halides produces the corresponding arylborohydrides in high yield.The arylborohydrides are readily hydrolyzed to the arylboronic acids.The syntheses are conveniently carried out in one pot.The reaction mechanism was clarified via a boron-11 NMR study.
- Kabalka, George W.,Sastry, Usha,Sastry, K.A.R.,Knapp, Furn F.,Srivastava, Prem C.
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p. 269 - 274
(2007/10/02)
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