- A Tethered Tolane: Twisting the Excited State
-
The synthesis of a doubly bridged tolane is reported. The target is obtained in a five-step synthesis, starting from commercially available 2-amino-meta-xylene by a combination of a Sandmeyer reaction, radical bromination, and Stille-type coupling, followed by double ring closing. The doubly tethered tolane is crystalline; the two phenyl rings are highly twisted with respect to each other both in solution and in the solid state. Optical spectroscopy and quantum chemical calculations show that the doubly bridged tolane is twisted not only in the ground state, but also in the excited state, leading to emission from the twisted state in solution and in the solid state. Strong phosphorescence is observed at cryogenic temperatures.
- Kozhemyakin, Yury,Kr?mer, Maximilian,Rominger, Frank,Dreuw, Andreas,Bunz, Uwe H. F.
-
-
Read Online
- 2-Bromo-1,3-bis(bromomethyl)-benzene, with Z′ = 1.5: Whole-molecule disorder of one of the two independent molecules
-
The title compound, C8H7r3, possesses normal geometrical parameters. There are two independent molecules; one shows whole-molecule disorder with respect to an inversion-symmetry-generated partner, while the other is undiso
- Kirsop, Peter,Storey, John M. D.,Harrison, William T. A.
-
-
Read Online
- A Convenient New Synthesis of Benzo[a]pyrene
-
A convenient new synthesis of the ubiquitous environmental carcinogen benzo[a]pyrene (BaP) is described. In the key step, the method entails Suzuki coupling of naphthalene 2-boronic acid with 2-bromobenzene-1,3-dialdehyde and requires only three steps. It is considerably shorter and simpler than the older methods and provides BaP in higher overall yield.
- Harvey, Ronald G.,Lim, Keunpoong,Dai, Qing
-
-
Read Online
- Synthesis and biological evaluation of thielocin B1 analogues as protein-protein interaction inhibitors of PAC3 homodimer
-
The synthesis and biological evaluation of thielocin B1 analogues have been demonstrated. Fourteen analogues modified in the central core and terminal carboxylic acid moiety were concisely synthesized by simple esterification or etherification reaction. The evaluation of synthetic analogues as inhibitors of proteasome assembling chaperone (PAC) complexes (the PAC3 homodimer and PAC1/PAC2) revealed that the natural product-like bending structure and terminal carboxylic acid groups were crucial for its biological activity. Moreover, SAR and in silico docking studies indicated that all methyl groups on the diphenyl ether moiety of thielocin B1 contribute to the potent and selective inhibition of the PAC3 homodimer via hydrophobic interactions.
- Ohsawa, Kosuke,Yoshida, Masahito,Izumikawa, Miho,Takagi, Motoki,Shin-ya, Kazuo,Goshima, Naoki,Hirokawa, Takatsugu,Natsume, Tohru,Doi, Takayuki
-
p. 6023 - 6034
(2018/11/23)
-
- PYRROLO SULFONAMIDE COMPOUNDS FOR MODULATION OF ORPHAN NUCLEAR RECEPTOR RAR-RELATED ORPHAN RECEPTOR-GAMMA (RORGAMMA, NR1F3) ACTIVITY AND FOR THE TREATMENT OF CHRONIC INFLAMMATORY AND AUTOIMMUNE DISEASES
-
The invention provides modulators for the orphan nuclear receptor RORy and methods for treating RORy mediated diseases by administrating these novel RORy modulators to a human or a mammal in need thereof. Specifically, the present invention provides pyrrolo sulfonamide compounds of Formula (1) and the enantiomers, diastereomers, tautomers, solvates and pharmaceutically acceptable salts thereof.
- -
-
Page/Page column 36
(2012/11/06)
-
- Synthetic scope, computational chemistry and mechanism of a base induced 5-endo cyclization of benzyl alkynyl sulfides
-
We present an experimental and computational study of the reaction of aryl substituted benzyl 1-alkynyl sulfides with potassium alkoxide in acetonitrile, which produces 2-aryl 2,3-dihydrothiophenes in poor to good yields. The cyclization is most efficient with electron withdrawing groups on the aromatic ring. Evidence indicates there is rapid exchange of protons and tautomerism of the alkynyl unit prior to cyclization. Theoretical calculations were also conducted to help rationalize the base induced 5-endo cyclization of benzyl 1-propynyl sulfide (1a). The potential energy surface was calculated for the formation of 2,3-dihydrothiophene in a reaction of benzyl 1-propynyl sulfide (1a) with potassium methoxide. Geometries were optimized with CAM-B3LYP/6-311+G(d,p) in acetonitrile with the CPCM solvent model. It is significant that the benzyl propa-1,2-dien-1-yl sulfane (6) possessed a lower benzylic proton affinity than the benzyl prop-2-yn-1-yl sulfane (8) thus favoring the base induced reaction of the former. From benzyl(propa-1,2-dien-1- yl sulfane (6), 2,3-dihydrothiophene can be formed via a conjugate base that undergoes 5-endo-trig cyclization followed by a protonation step.
- Motto, John M.,Castillo, álvaro,Greer, Alexander,Montemayer, Laura K.,Sheepwash, Erin E.,Schwan, Adrian L.
-
supporting information; experimental part
p. 1002 - 1010
(2011/03/19)
-
- Bronsted base-assisted boronic acid catalysis for the dehydrative intramolecular condensation of dicarboxylic acids
-
Bronsted base-assisted boronic acid catalysis for the dehydrative self-condensation of carboxylic acids is described. Arylboronic acid bearing bulky (N,N-dialkylamino)methyl groups at the 2,6-positions can catalyze the intramolecular dehydrative condensation of di-and tetracarboxylic acids. This is the first successful method for the catalytic dehydrative self-condensation of carboxylic acids.(Figure Presented)
- Sakakura, Akira,Ohkubo, Takuro,Yamashita, Risa,Akakura, Matsujiro,Ishihara, Kazuaki
-
supporting information; experimental part
p. 892 - 895
(2011/05/02)
-
- METHOD FOR PRODUCING CARBOXYLIC ANHYDRIDE AND ARYLBORONIC ACID COMPOUND
-
When phthalic acid is heated in heptane under azeotropic reflux conditions in the presence of a catalytic amount of an arylboronic acid compound (such as 2,6-(diisopropylaminomethyl)phenylboronic acid or 2,6-bis(diisopropylaminomethyl)phenylboronic acid), phthalic anhydride is obtained in high yield.
- -
-
Page/Page column 8
(2012/01/13)
-
- Nucleophilic aryl fluorination and aryl halide exchange mediated by a CuI/CuIII catalytic cycle
-
Copper-catalyzed halide exchange reactions under very mild reaction conditions are described for the first time using a family of model aryl halide substrates. All combinations of halide exchange (I, Br, Cl, F) are observed using catalytic amounts of Cus
- Casitas, Alicia,Canta, Merce,Sola, Miquel,Costas, Miquel,Ribas, Xavi
-
supporting information; experimental part
p. 19386 - 19392
(2012/01/15)
-
- Highly twisted triarylamines for photoinduced intramolecular charge transfer
-
9-(N,N-Dianisylamino)anthracene (9DAAA), 9-(N,N-dianisylamino)dinaphth([1, 2-a:2′-1′-j]-anthracene (9DAAH), and 9,10-bis(N,N-dianisylamino) anthracene (910BAA) were synthesized as highly twisted triarylamines with potential for photoexcited internal charg
- Chudomel, J. Matthew,Yang, Boqian,Barnes, Michael D.,Achermann, Marc,Mague, Joel T.,Lahti, Paul M.
-
scheme or table
p. 8361 - 8368
(2011/10/17)
-
- Cross-coupling reaction of alcohols for carbon-carbon bond formation using pincer-type NHC/palladium catalysts
-
A cross-coupling reaction of different alcohols was achieved using a pincer-type NHC/PdBr complex as the catalyst precursor, and the reaction, under either Ar or H2 gas, displayed a broad substrate scope with respect to both primary and secondary alcohol components, with high alcohol product selectivity. The Royal Society of Chemistry 2010.
- Kose, Osamu,Saito, Susumu
-
supporting information; experimental part
p. 896 - 900
(2010/06/20)
-
- Synthesis of a 6-aryloxymethyl-5-hydroxy-2,3,4,5-tetrahydro-[1H]-2- benzazepin-4-one: A muscarinic (M3) antagonist
-
A synthesis of the racemic 6-aryloxymethyl-5-hydroxy-2,3,4,5-[1H]-2- tetrahydrobenzazepin-4-one 2, for evaluation as a muscarinic (M3) antagonist, is described. 2-[2-tert-Butyldimethylsilyloxymethyl-6-(2,6- dimethoxyphenoxymethyl)phenyl]propan-
- Evans, Paul,Lee, Alan T. L.,Thomas, Eric J.
-
supporting information; experimental part
p. 2158 - 2167
(2009/02/01)
-
- Synthesis of the o-Quinones and Other Oxidized Metabolites of Polycyclic Aromatic Hydrocarbons Implicated in Carcinogenesis
-
Efficient new syntheses of the o-quinone derivatives of benzo[a]pyrene (BPQ), 7,12-dimethylbenz-[a] anthracene (DMBAQ), and benz[a]anthracene (BAQ), implicated as active carcinogenic metabolites of the parent polycyclic aromatic hydrocarbons (PAHs), are reported. These PAH quinones also serve as starting compounds for the synthesis of the other active metabolites of these PAHs thought to be involved in their mechanism(s) of carcinogenesis. The latter include the corresponding o-catechols, trans-dihydrodiols, and the corresponding anti- and syn-diol epoxides.
- Harvey, Ronald G.,Dai, Qing,Ran, Chongzhao,Penning, Trevor M.
-
p. 2024 - 2032
(2007/10/03)
-
- First detection of a selenenyl fluoride ArSe-F by NMR spectroscopy: The nature of Ar2Se2/XeF2 and ArSe-SiMe 3/XeF2 reagents
-
Arylselenenyl fluorides ArSeF are obtained from diselenides Ar 2Se2 or arylselenotrimethylsilanes ArSe-SiMe3, and XeF2. They are detected by low-temperature 19F and 77Se NMR spectroscopy. Substitution in the ortho position of the aromatic ring to provide electronic or steric protection is a requirement for their formation. ArSe-F compounds decompose according to 3 ArSe-F → [ArSe-SeF2Ar] + ArSe-F- → ArSeF3 + Ar 2Se2. Reaction energies for this disproportionation as well as that of the sulfur and tellurium homologues have been calculated with MP2, CCSD(T,) and B3 LYP methods. They were found to be increasingly exothermic in the sequence S 77Se and 19F chemical shifts have been calculated by GIAO-MP2 and GIAO-B3LYP methods and are in good agreement with experimental values.
- Poleschner, Helmut,Seppelt, Konrad
-
p. 6565 - 6574
(2007/10/03)
-
- An EPR study of the intramolecular dynamics in o-semiquinonic nickel complexes with a diphosphorous pincer ligand
-
Square pyramidal o-semiquinonic nickel complexes with 2,6- bis(diphenylphosphinomethyl)phenyl have a flexible coordination sphere and exist in solution as the mixture of tautomers rapidly, according to EPR time scale, interconverting at room temperature.
- Kozhanov, Konstantin A.,Bubnov, Michael P.,Cherkasov, Vladimir K.,Fukin, Georgy K.,Abakumov, Gleb A.
-
p. 2610 - 2611
(2007/10/03)
-
- Binuclear complexes with ligands based on the 2,6-bis(diphenylphosphinomethyl)benzene framework. Syntheses and crystal structures of [Ir2Cl2(μ-CO){2,6-(Ph2PH2) 2C6H3S}2
-
The new binucleating phosphinothiolate proligand 2,6-(Ph2PCH2)C6H4SH (L3H) was prepared from bromo-2,6-dimethylbenzene in a 4 step synthesis. Reaction with [IrCl(CO)(PPh3)2] in MeCN gave th
- Dilworth, Jonathan R.,Zheng, Yifan,Griffiths, D. Vaughan
-
p. 1877 - 1881
(2007/10/03)
-
- Synthesis of chiral crown ethers having bromoarylene moieties on their rim. Anomalous behavior of racemic substrates in cyclization to crown ethers
-
Bis(binaphtho)-22-crown-5 and bis(binaphtho)-22-crown-4, having bromoarylene moities on their rim, were prepared from (R)- and (5)-2,2′-dihydroxy-1,1′-binaphthyl. An acyclic diol, bridged by two (R)-binaphthyl moieties, underwent cyclization reaction with
- Kiyooka, Syun-Ichi,Tada, Mitsuhiro,Kan, Sachie,Fujio, Mizue
-
p. 2595 - 2601
(2007/10/03)
-
- Synthesis, Conformation, and the Stereoselective Sulfur Extrusion Reaction of a New Intraanular Dibromo-Substituted Tetrathiametacyclophane
-
The oxidative coupling of 2,6-bis(mercaptomethyl)bromobenzene using I2 gave syn- and anti-10,20-dibromo-2,3,12,13-tetrathiametacyclophane (1) which can be isolated in the solid state at room temperature.The sulfur extrusion reaction of anti-1 with (E
- Fujihara, Hisashi,Chiu, Jer-Jye,Furukawa, Naomichi
-
p. 141 - 144
(2007/10/02)
-
- Intraanular phenyl-substituierte Phane - Synthese und dynamische Stereochemie
-
The synthesis and properties of phanes of different ring size, substituted intraanularly by phenyl groups, and of new biphenylophanes 3, 38 - 43 with "pseudo-syn/anti"-structure are described.Barriers for the hindered rotation of intraanular phenyl substituents have been determined by D-NMR spectroscopy. syn/anti conformers of -, -, - and metacyclophanes are found.A better method for the preparation of mediocyclic bisdisulfides is reported.The pyrolysis of (2-biphenylyl)methyl sulfones leads to fluorenes; pyrolysis of the thiosulfonic S-ester 44 yields bibenzyl and dibenzyl sulfide.
- Boeckmann, Klaus,Voegtle, Fritz
-
p. 1048 - 1064
(2007/10/02)
-