- Induction of one-handed helix sense in achiral poly(N-propargylamides)
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Achiral N-propargylamides, i.e., N-propargyl-3-methylbutanamide (1), N-propargyl-2-ethylbutanamide (2), and N-propargyl-3,3-dimethylbutanamide (3), were polymerized with (nbd)Rh+[η6-C6H5B- (C6H5)] to afford polymers with moderate molecular weights (Mn = 6000-22000) in good yields. The 1H NMR and UV-vis spectra demonstrated that the polymers, poly(1)-poly(3), have stereoregular structures (cis = 100%) and equally populated right- and left-handed helical conformation. A predominant helix sense was induced in these polymers by the addition of chiral alcohols or amine, which was confirmed by CD and UV-vis spectroscopies. 1H NMR and CD spectroscopic studies strongly suggested that the poly(N-propargylamides) interacted with the chiral alcohols by hydrogen bonding at the amide groups of the polymer side chain. Chiral terpenes could also induce single-handed helical conformation. It is likely that hydrophobic interaction led to the one-handed helical conformation in the case of the chiral terpenes because the addition of n-hexane decreased the CD signal.
- Tabei, Junichi,Nomura, Ryoji,Sanda, Fumio,Masuda, Toshio
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Read Online
- SMALL MOLECULE PROSTAGLADIN TRANSPORT INHIBITORS
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The disclosure provides compounds of Formula 1, and the pharmaceutically acceptable salts thereof. The variables in Formula 1, e.g. X1-X5, A1, A2, and R1-R4 are described herein. Such compounds are useful as prostaglandin transport (PGT) inhibitors. The disclosure further includes pharmaceutical compositions comprising a compound of Formula 1 or salt thereof and methods of using compounds of Formula 1 and salts thereof to treat diseases and disorders mediated, at least in part, by prostaglandin levels or cyclooxygenase activity. Such diseases and disorders include painful and inflammatory conditions.
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Paragraph 0260-0261
(2021/05/15)
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- Transition metal complex, polymer, mixture, composition and organic electronic device
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The invention discloses a transition metal complex, a polymer, a mixture, a composition and an organic electronic device. According to the transition metal complex, due to the fact that the metal organic complex contains a ketone group and has excellent electron transmission capacity, the compound contains an arylamine group and also has excellent hole transmission capacity, and the transition metal complex has a stable six-membered ring structure, when the transition metal complex serves as a light-emitting layer doping material and is applied to an organic electronic device, especially an OLED, the light-emitting efficiency of the device can be improved, and the service life of the device can be prolonged.
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Paragraph 0259-0260; 0265-0266
(2021/06/23)
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- Palladium-Catalyzed Migratory Insertion of Carbenes and C-C Cleavage of Cycloalkanecarboxamides
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A palladium catalyzed reaction of cycloalkanecarboxamides and diazomalonates or bis(phenylsulfonyl)diazomethane has been developed. The reaction proceeds via carbene migratory insertion and cascade C-C cleavage pathways. Cycloalkanecarboxamides with four to seven membered rings are applicable in the transformation. A series of ring opening products were prepared with moderate yields. The finding provides valuable clues for the development of new reactions involving carbene migratory insertion and the cleavage of unstrained C(sp3)-C(sp3) bonds.
- Pan, Ping,Yan, Ming,Zeng, Jia,Zhang, Peng,Zhang, Xue-Jing
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supporting information
(2022/01/20)
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- Organic luminescent material containing 6-silicon-based substituted isoquinoline ligand
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Disclosed is an organic light-emitting material containing a 6silicon-based substituted isoquinoline ligand. The organic light-emitting material is a metal complex containing a 6silicon-based substituted isoquinoline ligand, and can be used as a light-emitting material in a light-emitting layer of an organic light-emitting device. These novel complexes can provide more red and saturated emissions,and can also exhibit significantly improved lifetime and high efficiency excellent device performance. An electroluminescent device and a compound formulation comprising the metal complex are also disclosed.
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Paragraph 0159; 0169-0171
(2020/11/22)
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- Metal complex containing three different ligands
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A metal complex containing three different ligands is disclosed. The metal complex contains three different ligands, and can be used as a luminescent material in a luminescent layer of an organic electroluminescent device. The novel complexes not only can achieve the device performance expected to be regulated or improved by regulating substituent groups, but also can achieve the effect of effectively controlling the rise of the evaporation temperature. An electroluminescent device and a compound formulation comprising the metal complex are also disclosed.
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Paragraph 0142; 0152-0154
(2020/11/22)
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- Enantio- and Diastereoswitchable C?H Arylation of Methylene Groups in Cycloalkanes
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A complementary set of chiral N,N-ligands enables the Pd-catalyzed β-C?H arylation of unbiased internal methylene groups in good yield and with high levels of enantio- and diastereoinduction. Both the dia- and enantioselectivity can be reversed, thus allowing the selective arylation of any of the four β-C?H bonds in cycloalkanecarboxamides of various ring sizes. The method is applicable to a broad range of aryl iodides with electron-withdrawing and -donating substituents in the o-, m-, or p-position.
- Andr?, Michal S.,Schifferer, Lukas,Pollok, Corina H.,Merten, Christian,Goo?en, Lukas J.,Yu, Jin-Quan
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supporting information
p. 8503 - 8507
(2019/07/16)
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- Synthesis of 1,3-Diketones and β-Keto Thioesters via Soft Enolization
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Ketones and thioesters undergo soft enolization and acylation using crude acid chlorides on treatment with MgBr2·OEt2 and i-Pr2NEt to give 1,3-diketones and β-keto thioesters, respectively. The use of crude acid chlorides adds efficiency and cost reduction by avoiding the need to purify and/or purchase them. The process is conducted in a direct fashion that does not require prior enolate formation, further enhancing its efficiency and making it very easy to carry out. The method is suitable for large scale applications. ?
- Aderibigbe, Sabrina O.,Coltart, Don M.
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p. 9770 - 9777
(2019/08/27)
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- Direct C-C Bond Formation from Alkanes Using Ni-Photoredox Catalysis
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A method for direct cross coupling between unactivated C(sp3)-H bonds and chloroformates has been accomplished via nickel and photoredox catalysis. A diverse range of feedstock chemicals, such as (a)cyclic alkanes and toluenes, along with late-stage intermediates, undergo intermolecular C-C bond formation to afford esters under mild conditions using only 3 equiv of the C-H partner. Site selectivity is predictable according to bond strength and polarity trends that are consistent with the intermediacy of a chlorine radical as the hydrogen atom-abstracting species.
- Ackerman, Laura K. G.,Martinez Alvarado, Jesus I.,Doyle, Abigail G.
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p. 14059 - 14063
(2018/10/24)
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- Bidentate ligand 8-aminoquinoline-aided Pd-catalyzed diastereoselective β-arylation of the prochiral secondary sp3 C-H bonds of 2-phenylbutanamides and related aliphatic carboxamides
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Investigations on the Pd-catalyzed 8-aminoquinoline-aided diastereoselective β-arylation of the prochiral 2° sp3 C-H bonds of various aliphatic carboxamides having substituents at the α- or γ-positions are reported. The Pd-catalyzed β-arylation of the 2° sp3 C-H bonds of racemic 2-phenylbutanamides with aryl iodides gave the arylated products (±)-3a-l (anti isomers) with moderate to good diastereoselectivities (dr up to 86:14). Next, the Pd-catalyzed β-arylation of various γ-substituted aliphatic carboxamides with aryl iodides furnished the corresponding C-H arylated products with poor diastereoselectivities. Then, the arylation of the C(β)-H bonds of 2-ethyl-N-(quinolin-8-yl)butanamide possessing two prochiral centers with aryl iodides successfully furnished the bis arylated products meso-8eA-hA and (±)-8eB-hB (diastereomers). The arylation of (S)-2-phenylbutanamide also gave the corresponding enantiomerically enriched compounds 10a-c (anti isomers). The stereochemistry of the products (±)-3a-l (major isomers), meso-8eA-hA (major isomers), (±)-8eB-hB (minor isomers) and enantiomerically enriched compounds 10a-c (major isomers) were assigned based on the X-ray structures of the major isomers 3b,c,e,l, 8eA, 10c and minor isomers 8eB and 8fB. The limitations and outcome of the stereocontrol in the Pd-catalyzed C-H arylation reactions involving aliphatic carboxamides are illustrated.
- Gopalakrishnan, Bojan,Babu, Srinivasarao Arulananda,Padmavathi, Rayavarapu
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p. 8333 - 8349
(2015/10/05)
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- Ligand-enabled methylene C(sp3)-H bond activation with a Pd(II) catalyst
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Pd(II) insertion into β-methylene C(sp3)-H bonds was enabled by a mutually repulsive and electron-rich quinoline ligand. Ligand tuning led to the development of a method that allows for installation of an aryl group on a range of acyclic and cyclic amides containing β-methylene C(sp3)-H bonds.
- Wasa, Masayuki,Chan, Kelvin S. L.,Zhang, Xing-Guo,He, Jian,Miura, Masanori,Yu, Jin-Quan
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supporting information
p. 18570 - 18572
(2013/01/15)
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- Syntheses and evaluation of anticonvulsant profile and teratogenicity of novel amide derivatives of branched aliphatic carboxylic acids with 4-aminobenzensulfonamide
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Despite the availability of 14 new antiepileptic drugs (AEDs), about 30% of epileptic patients are not seizure-free. Consequently there is substantial need to develop new effective AEDs. A novel class of aromatic amides composed of phenylacetic acid or branched aliphatic carboxylic acids, with five to nine carbons in their carboxylic moiety, and aminobenzenesulfonamide were synthesized and evaluated in the anticonvulsant rat-maximal electroshock (MES) and subcutaneous metrazol seizure (scMet) tests. Fourteen of the synthesized amides had an anticonvulsant ED50 of 50 values of 7.6, 9.9, and 9.4 mg/kg and remarkable protective index (PI = TD 50/ED50) values of 65.7, 50.5, and 53.2, respectively. These potent sulfanylamides caused neural tube defects only at doses markedly exceeding their effective dose. The anticonvulsant properties of these compounds make them potential candidates for further development as new, potent, and safe AEDs.
- Hen, Naama,Bialer, Meir,Wlodarczyk, Bogdan,Finnell, Richard H.,Yagen, Boris
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scheme or table
p. 4177 - 4186
(2010/09/04)
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- Cyano diels-alder and cyano ene reactions. Applications in a formal [2 + 2 + 2] cycloaddition strategy for the synthesis of pyridines
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Two metal-free, formal [2 + 2 + 2] cycloaddition strategies for the construction of polycyclic pyridine derivatives are described that proceed via pericyclic cascade mechanisms featuring the participation of unactivated cyano groups as enophile and dienophile cycloaddition partners.
- Sakai, Takeo,Danheiser, Rick L.
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supporting information; experimental part
p. 13203 - 13205
(2010/11/05)
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- Synthesis and evaluation of antiallodynic and anticonvulsant activity of novel amide and urea derivatives of valproic acid analogues
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Valproic acid (VPA, 1) is a major broad spectrum antiepileptic and central nervous system drug widely used to treat epilepsy, bipolar disorder, and migraine. VPA's clinical use is limited by two severe and lifethreatening side effects, teratogenicity and hepatotoxicity. A number of VPA analogues and their amide, N-methylamide and urea derivatives, were synthesized and evaluated in animal models of neuropathic pain and epilepsy. Among these, two amide and two urea derivatives of 1 showed the highest potency as antineuropathic pain compounds, with ED50 values of 49 and 51 mg/kg for the amides (19 and 20) and 49 and 74 mg/kg for the urea derivatives (29 and 33), respectively. 19, 20, and 29 were equipotent to gabapentin, a leading drug for the treatment of neuropathic pain. These data indicate strong potential for the above-mentioned novel compounds as candidates for future drug development for the treatment of neuropathic pain. 2009 American Chemical Society.
- Kaufmann, Dan,Bialer, Meir,Shimshoni, Jakob Avi,Devor, Marshall,Yagen, Boris
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scheme or table
p. 7236 - 7248
(2010/07/04)
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- PENEM PRODRUGS
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Orally bioavailable prodrugs of sulopenem, e.g., and solvates and hydrates thereof, preparation thereof, formulation thereof, and use to treat and prevent infection in mammals such as humans. This abstract is not limiting to the invention.
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Page/Page column 17-18
(2008/06/13)
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- Dynamically stable helices of poly(N-propargylamides) with bulky aliphatic groups
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N-Propargylamides with bulky pendent groups [HC≡CCH2NHCOR, 9: R = CH2C(CH3)3, 10: R=C(CH 3)3 11: R = C(CH3)2CH 2CH2CH3,12: R = CH(CH2CH 3)2, 13: R = CH(CH2CH2CH 3)2] were polymerized with a rhodium catalyst, (nbd)Rh+B-(C8H5)4 (nbd = 2,5-norbornadiene), to obtain the polymers in 80-92% yields. Poly(11) and poly(12) possessed moderate molecular weights (Mn ≥ 10 000) and were totally soluble in a few solvents including chloroform. On the other hand, the Mn values of poly(9), poly(10), and poly(13) were no more than 5000, and these polymers were not completely soluble in any solvents. The conformational transition behavior of these polymers was examined by temperature-variable UV-vis spectroscopy in chloroform solution, which revealed that poly(10) - poly(13) could form dynamically stable helical conformation even at 60°C. By copolymerizations of monomers 9 and 10 with monomer 4, HC≡CCH2NHCO(CH2)4H, the solubility of the polymers was effectively improved and almost all the copolymers totally dissolved in chloroform, while the molecular weights of the copolymers increased up to 18 600-45 000. Moreover, the helix contents of poly(40.63-co- 90.37) and poly(40.40-co-100.60) were the highest among the two series of (co)polymers, respectively. It is concluded that the copolymerization of 9 and 10 with 4 effectively decreased the steric repulsion between the crowded side chains, which probably allowed the copolymers to take helical conformation efficiently.
- Deng, Jianping,Tabei, Junichi,Shiotsuki, Masashi,Sanda, Fumio,Masuda, Toshio
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p. 5149 - 5154
(2007/10/03)
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- SELECIVE SYNTHESIS OF 3-BULKYALKYLSUBSTITUTED 5-AMINOISOXAZOL
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Methyl 2-ethylbutyrate (3) plus lithiumdiisopropylamide reacted with methyl iodide to give methyl 2-ethyl-2-methylbutyrate (4).The methylene carbanion of acetonitrile-generated with lithiumdiisopropylamide- reacted with 4 to give 4-ethyl-4-methyl-3-oxohexanenitrile (5). 3-Ketonitrile 5 reacted with hydroxylamine after 20 min of heating to reflux in ethanol to give 4-ethyl-4-methyl-3-oxoheyanitrile oxime (6).This in aqueous dilute HCl was selectively and quantitatively transformed into 5-amino-3-(1-ethyl-1-methylpropyl)-isoxazol (7).Longer heating of 5 with hydroxylamine directly generated a mixture of 7 with its isomer 3-amino-5-(1-ethyl-1-methylpropyl)isoxazol (7b).Reaction conditions were studied for optimization of the 5-aminoisoxazol 7 synthesis.
- Rouchaud, J.,Gustin, F.,Moulard, C.
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p. 545 - 556
(2007/10/02)
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- Alkyl Group Effects on the Rate Constants and Equilibrium Constants for Formation of Cyclic Tetrahedral Intermediates
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2-Hydroxy-2-alkyl-1,3-dioxolanes T are the cyclic intermediates of the degenerate intramolecular ester interchange reactions of ethylene glycol monoalkanoates A, in which alkanoyl groups transfer from one end of ethylene glycol to the other.This study reports equilibrium constants for the cyclization AT to the tetrahedral intermediate stage with 10 alkanoate derivatives.These equiilibrium constants, which when written as / are all large (1 E7-1 E9) in favor of the ring opened form, were obtained as the ratio of rate constants for equilibration occuring with H+ catalysis.Rate constants for the ring opening of T were directly measured through a study of kinetics of the hydrolysis of 2-methoxy-2-alkyl-1,3-dioxolane ortho esters.These hydrolysis proceed via T, and under acid conditions the breakdown of this intermediate is rate-limiting.Rate constants in the ring-closing direction were obtained by preparing HOCH2CD2OOCR and, with the use of 1H NMR spectroscopy, measuring the kinetics of isomerization to an equilibrium mixture with RCOOCH2CD2OH.The reaction under investigation is an intramolecular analogue of H+-catalyzed alkanoate ester hydrolysis, whose rate constant define the steric substituent parameter Es.The ring-closure rate constant for A -> T do show an excellent correlation with Es.However, the rate constants for ring-opening T -> A and the overall equilibrium constant are badly correlated, showing quite different behavior for series with α and β branching in the alkyl group.Thus, for this system the Es parameter does not correlate free energy differencies between the acyl derivative and tetrahedral intermediate.It is only the free energy differences between the acyl form and the transition state leading to the intermediate that fit Es.
- Santry, Linda J.,Azer, Salwa,McClelland, Robert A.
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p. 2909 - 2914
(2007/10/02)
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- NOUVELLES METHODES DE DESHALOGENATION ET DE FORMATION D'ETHERS D'ENOL TRIMETHYLSILYLIQUES PAR ACTION DE iPr2NLi SUR QUELQUES α-MONOBROMO- ET α,α'-DIBROMOCETONES
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Attempts to prepare 2-bromo-2,4-dimethyl,3-trimethylsiloxy 3-pentene reacting lithium diisopropylamide (LDA) with 2-bromo-2,4-dimethyl-3 pentanone have revealed two new reactions.After a few minutes quantitative yields are obtained of either the dehalogenated ketone (after hydrolysis) or the trimethylsilyl enol ether (after addition of trimethylsilyl chloride).These reactions are general and have been extended to other α-monobromoketones and α,α'-dibromoketones.In the latter case, the reaction is more complex and leads generally to dehalogenation or reduction products.
- Lion, Claude,Dubois, Jacques-Emile,Lebbar, Khadija
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p. 119 - 126
(2007/10/02)
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- CONDENSATION DES ORGANOMAGNESIENS SUR LES CHLORUSES D'ACIDE DANS LE TETRAHYDROFURANNE A BASSE TEMPERATURE
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The condensation of a Grignard reagents with hindered acid chlorides in THF at low temperature, yields ketones which are generally difficult to obtain and avoids the side reaction caused with a CuCl catalyst.Applied to unsaturated Grignard reagents and acid chlorides, this method also yields unsaturated ketones, such as the Artemisia ketone.
- Dubois, Jacques-Emile,Lion, Claude,Arouisse, Abdelmajid
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p. 1083 - 1088
(2007/10/02)
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- Acylation de quelques olefines substituees selon Friedel-Crafts. Synthese de cetones insaturees encombrees
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The Friedel-Crafts acylation of olefins by acid chlorides has been carried out on very heavily substituted olefins.Coupled by catalytic hydrogenation this reaction allows, in principle, the synthesis of hindered saturated ketones.Compounds of the type tBuiPrCHCOCHiPr2 (2221) (2220) tBuiPrCHCOCHiPrtBu (2221) (2221) and tBu2CHCOCHiPrtBu (2222) (2221) which are impossible to obtain by other methods, become accessible.
- Dubois, Jacques-Emile,Saumtally, Imran,Lion, Claude
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p. 133 - 138
(2007/10/02)
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- 2-Acyl-3-substituted cyclopentan-1-ones and process for their preparation
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1,3-Dicarbonyl compounds useful as medicines, agricultural chemicals, perfumes, and their intermediates are prepared by reacting a specific α,β-unsaturated carbonyl compound with a specific organic copper lithium compound in the presence of an aprotic inert organic solvent, and then reacting the reaction product with an organic carboxylic acid halide or anhydride. In particular, novel 2-acyl-3-substituted cyclopentan-1-ones and 2-acyl-3-substituted cyclohexan-1-ones having important physiological activities are provided.
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