- Gold Catalysts Can Generate Nitrone Intermediates from a Nitrosoarene/Alkene Mixture, Enabling Two Distinct Catalytic Reactions: A Nitroso-Activated Cycloheptatriene/Benzylidene Rearrangement
-
Gold-catalyzed reactions of cycloheptatrienes with nitrosoarenes yield nitrone derivatives efficiently. This reaction sequence enables us to develop gold-catalyzed aerobic oxidations of cycloheptatrienes to afford benzaldehyde derivatives using CuCl and nitrosoarenes as co-catalysts (10-30 mol %). Our density functional theory calculations support a novel nitroso-activated rearrangement, tropylium → benzylidene. With the same nitrosoarenes, we developed their gold-catalyzed [2 + 2 + 1]-annulations between nitrosobenzene and two enol ethers to yield 5-alkoxyisoxazolidines using 1,4-cyclohexadienes as hydrogen donors.
- Cheng, Mu-Jeng,Kardile, Rahul Dadabhau,Kuo, Tung-Chun,Liu, Rai-Shung,More, Sayaji Arjun
-
supporting information
p. 5506 - 5511
(2021/07/31)
-
- Piperidine compound and preparation method and medical application thereof
-
The invention discloses a piperidine compound shown as a formula (I) and a preparation method and medical application thereof, and particularly relates to a piperidine USP7 inhibitor compound or pharmaceutically acceptable salt or ester or solvate thereof and a preparation method and application of the piperidine USP7 inhibitor compound or pharmaceutically acceptable salt or ester or solvate thereof. The compound provided by the invention can inhibit the activity of USP7 enzyme, has very good selectivity and druggability, and can be used for preparing medicines for preventing or treating tumor diseases or virus infectious diseases.
- -
-
Paragraph 0574; 0585-0588
(2021/04/07)
-
- Synthesis of Substituted Benzaldehydes via a Two-Step, One-Pot Reduction/Cross-Coupling Procedure
-
The synthesis of functionalized (benz)aldehydes, via a two-step, one-pot procedure, is presented. The method employs a stable aluminum hemiaminal as a tetrahedral intermediate, protecting a latent aldehyde, making it suitable for subsequent cross-coupling with (strong nucleophilic) organometallic reagents, leading to a variety of alkyl and aryl substituted benzaldehydes. This very fast methodology also facilitates the effective synthesis of a 11C radiolabeled aldehyde. Aluminum-ate complexes enable transmetalation of alkyl fragments onto palladium and subsequent cross-coupling.
- Heijnen, Dorus,Helbert, Hugo,Luurtsema, Gert,Elsinga, Philip H.,Feringa, Ben L.
-
supporting information
p. 4087 - 4091
(2019/06/14)
-
- Effective bimetallic composite catalysts for the synthesis of arylated furans and thiophenes in aqueous media
-
[Figure not available: see fulltext.] N-(4,6-Dimethylpyrimidin-2-yl)-5-phenylisoxazole-3-carboxamide was used as a ligand for obtaining bimetallic boron-containing heterogeneous catalysts Pd–Ni(Co)–B–L (Ni(Co):Pd = 9:1). The obtained composites were highl
- Bumagin, Nikolay A.,Petkevich, Sergey K.,Kletskov, Alexey V.,Alekseyev, Roman S.,Potkin, Vladimir I.
-
-
- Molecular Design of Donor-Acceptor-Type Organic Photocatalysts for Metal-free Aromatic C?C Bond Formations under Visible Light
-
Metal-free and photocatalytic radical-mediated aromatic C?C bond formations offer a promising alternative pathway to the conventional transition metal-catalyzed cross-coupling reactions. However, the formation of aryl radicals from common precursors such as aryl halides is highly challenging due to their extremely high reductive potential. Here, we report a structural design strategy of donor-acceptor-type organic photocatalysts for visible light-driven C?C bond formations through the reductive dehalogenation of aryl halides. The reduction potential of the photocatalysts could be systematically aligned to be ?2.04 V vs. SCE via a simple heteroatom engineering of the donor-acceptor moieties. The high reductive potential of the molecular photocatalyst could reduce various aryl halides into aryl radicals to form the C?C bond with heteroarenes. The designability of the molecular photocatalyst further allowed the synthesis of a high LUMO (lowest unoccupied molecular orbital) polymer photocatalyst by a self-initiated free radical polymerization without compromising its LUMO level. (Figure presented.).
- Wang, Lei,Byun, Jeehye,Li, Run,Huang, Wei,Zhang, Kai A. I.
-
p. 4312 - 4318
(2018/10/02)
-
- Copper diisobutyl-t-butoxyaluminum hydride: A novel reagent for chemoselective reduction of tertiary amides over esters
-
We demonstrate that copper diisobutyl-t-butoxyaluminum hydride, readily prepared from lithium diisobutyl-t-butoxyaluminum hydride and CuI, effectively and chemoselectively reduces tertiary amides over esters at ambient temperature, affording the corresponding aldehydes in excellent yields.
- Im, So Hee,Shin, Won Kyu,Jaladi, Ashok Kumar,An, Duk Keun
-
p. 2335 - 2340
(2018/05/16)
-
- Barbituric acid derivative of monosubtstituted five-membered heterocycle and preparation method thereof
-
The invention discloses a barbituric acid derivative of monosubtstituted five-membered heterocycle and a preparation method thereof. The chemical structural formula of the barbituric acid derivative is shown in the specification. The barbituric acid derivative based on thiophene or furan is synthesized for the first time, and it is found through an experiment that the derivative shows a solvationcolor change effect: along with increase of the solvent polarity, a fluorescence spectrum is in red shift.
- -
-
Paragraph 0037; 0049-0051; 0055
(2018/10/19)
-
- Palladacycles derived from arylphosphinamides for mild Suzuki-Miyaura cross-couplings
-
We present a type of palladacyclic complexes derived from arylphosphinamides which can be used as efficient and versatile precatalysts for mild Suzuki-Miyaura cross-coupling. With the presence of 1.0 mol% of palladacycles, a wide variety of aryl bromides and boronic acids could be coupled very efficiently at ambient temperature and under air atmosphere without the need of external supporting ligands. Moreover, the mild conditions also allow for smooth coupling of electron-deficient, i.e., the less stable aryl triflates. In addition to the highly catalytic activity, the palladacyclic complexes can be very easily prepared through a two-step procedure from the readily affordable diphenyl-phosphinic chloride and exhibit excellent stability toward air and moisture. Due to these prominent properties, the new palladacycles would find practical use in Suzuki-Miyaura couplings.
- Wu, Guo-Jie,Han, Fu-She,Zhao, Yu-Long
-
p. 69776 - 69781
(2015/09/01)
-
- Mild, green copper/4-dimethylaminopyridine catalysed aerobic oxidation of alcohols mediated by nitroxyl radicals in water
-
A novel copper/4-dimethylaminopyridine catalyst system has been found to catalyse the aerobic oxidation of a variety of primary and secondary alcohols in water at room temperature, in the presence of a TEMPO or ABNO nitroxyl radical. A tetranuclear CuII cluster was revealed to be a plausible reactive intermediate.
- Zhang, Guoqi,Yang, Chengxiong,Liu,Li, Li,Golen, James A.,Rheingold, Arnold L.
-
p. 61907 - 61911
(2015/02/19)
-
- An effective activation of palladium phosphine complexes in aqueous phase reactions of hetero-aromatic boronic acids with aryl halides
-
We have developed a simple and effective method for the activation of palladium phosphine complexes in the Suzuki reaction (TON up to 9800, TOF up to 58800 h-1) by selecting an aqueous reaction medium instead of organic solvents. This method wa
- Bumagin,Veselov,Belov
-
-
- 5-(Naphth-1-yl)- and 5-[(1,1'-biphenyl)-4-yl]isoxazole-3-carbaldehyde oximes: Synthesis, complexes with palladium, and application in catalysis
-
1-(Naphth-1-yl)- and 1-[(1,1'-biphenyl)-4-yl-3,4,4-trichloro-3-buten-1-ones were synthesized by acylation of naphthalene and biphenyl with 3,4,4-trichloro-3-butenoyl chloride. Further reaction with hydroxylamine led to 5-(naphth-1-yl)- and 5-[(1,1'-biphen
- Potkin,Bumagin,Zelenkovskii,Petkevich,Livantsov,Golantsov
-
p. 1782 - 1792
(2015/01/08)
-
- Pyrazole[3,4-e][1,4]thiazepin-7-one derivatives as a novel class of Farnesoid X Receptor (FXR) agonists
-
A virtual screening procedure was applied to the discovery of structurally diverse non-steroidal Farnesoid X Receptor (FXR) agonists. From 117 compounds selected by virtual screening, a total of 47 compounds were found to be FXR agonists, with 34 of them showing activity below a concentration of 20 μM. 1H-Pyrazole[3,4-e][1,4]thiazepin-7-one-based hit compound 7 was chosen for hit-to-lead optimization. A large number of 1H-pyrazole[3,4-e][1,4]thiazepin-7- one derivatives was designed, synthesized, and evaluated by a cell-based luciferase transactivation assay for their agonistic activity against FXR. Most of them exhibited low micromolar range of potency and very high efficacy.
- Marinozzi, Maura,Carotti, Andrea,Sansone, Emanuele,MacChiarulo, Antonio,Rosatelli, Emiliano,Sardella, Roccaldo,Natalini, Benedetto,Rizzo, Giovanni,Adorini, Luciano,Passeri, Daniela,De Franco, Francesca,Pruzanski, Mark,Pellicciari, Roberto
-
supporting information; experimental part
p. 3429 - 3445
(2012/07/30)
-
- Scope of the suzuki-Miyaura cross-coupling reactions of potassium heteroaryltrifluoroborates
-
A wide variety of bench-stable potassium heteroaryltrifluoroborates were prepared, and general reaction conditions were developed for their cross-coupling to aryl and heteroaryl halides. The cross-coupled products were obtained in good to excellent yields. This method represents an efficient and facile installation of heterocyclic building blocks onto preexisting organic substructures.
- Molander, Gary A.,Canturk, Belgin,Kennedy, Lauren E.
-
supporting information; experimental part
p. 973 - 980
(2009/07/11)
-
- Generation of aryl radicals from arylboronic acids by manganese(III) acetate: Synthesis of biaryls and heterobiaryls
-
The efficient generation of aryl radicals from arylboronic acids by manganese(III) acetate is described. In aromatic solvents, in situ generated aryl radicals afford the corresponding biaryls in very good yields. This method works selectively, and yields
- Demir, Ayhan S.,Reis, Oemer,Emrullahoglu, Mustafa
-
p. 578 - 580
(2007/10/03)
-
- C-C-Bond Formation by the Palladium-Catalyzed Cycloisomerization/Dimerization of Terminal Allenyl Ketones: Selectivity and Mechanistic Aspects
-
The scope of the palladium-catalyzed cyclization/dimerization of terminal allenyl ketones 1 to the 2,4-disubstituted furans 3 has been investigated. Simplified and improved conditions almost exclusively provided the dimer 3, accompanied by only traces of the easily separable monomer 2. The formation of an isomer of 3, the unconjugated ketone 4, was completeley suppressed. Under these mild conditions, besides the normal functional group tolerance known for palladium-catalyzed reactions, an interesting selectivity was observed with functional groups that are known to react either in palladium-catalyzed reactions or reactions catalyzed by other transition-metals. Thus aryl halides, terminal alkynes, 1,6-enynes, and α-allenic alcohols were tolerated. In the latter example the selective reaction of only one out of two different allenes was achieved. Mechanistic investigation indicated a Pd(II)/Pd(IV)-cycle involving palladium(II)-γ-alkoxyvinylcarbene and furylpalladium(IV) hydride intermediates, although a second pathway for the formation of the dimer 3 which also involves Pd(IV)-intermediates like the 3,4-dimethylenepalladacyclopentane 23 and the 3-methylenepalladacyclobutane-like structure 15 (respectively 25) could not completely be excluded.
- Hashmi, A. Stephen K.,Ruppert, Thorsten L.,Knoefel, Thomas,Bats, Jan W.
-
p. 7295 - 7304
(2007/10/03)
-
- PALLADIUM-CATALYZED ARYLATION OF FURAN, THIOPHENE, BENZOFURAN AND BENZOTHIOPHENE
-
Treatment of ?-electron sufficient aromatic heterocycles such as furan, thiophene, benzofuran and benzothiophene with aryl bromides in the presence of tetrakis(triphenyphosphine)palladium gave the corresponding 2-aryl aromatic heterocycles.
- Ohta, Akihiro,Akita, Yasuo,Ohkuwa, Teruya,Chiba, Mari,Fukunaga, Ryuichi,et al.
-
p. 1951 - 1958
(2007/10/02)
-