Cu(OAc)2-catalyzed direct radical C2 arylation of quinoline N-oxide with arylamines

A Cu(OAc)₂-catalyzed synthesis of 2-arylquinoline N-oxides with easily available arylamines is described. The main features of this reaction are mild reaction conditions, high functional-group tolerance, excellent regioselectivity, and good to excellent yields. This procedure is mild, operationally simple, and constitutes a greener approach to the arylation of quinoline N-oxides.     

Palladium-catalyzed direct arylation of 4-hydroxycoumarins with arylboronic acids via C-OH bond activation

Operationally simple PdCl₂-catalyzed direct arylation of 4-hydroxycoumarins with arylboronic acids via C-OH bond activation under mild conditions is described, which gave rise to the corresponding 4-arylcouamrins in good to excellent yields.     

ipso-Bromination/iodination of arylboronic acids: Poly(4-vinylpyridine)-Br2/I2 complexes as safe and efficient reagents

Poly(4-vinyl pyridine) supported bromine/iodine complexes were prepared and probed for ipso-bromination/iodination of arylboronic acids. These solid complexes with catalytic amount of additive are found to be safe and efficient reagent system for the ipso-bromination/iodination. The reaction occurs under mild conditions and tolerates various functional groups resulting in products with high selectivity and yields.     

A nickel precatalyst for efficient cross-coupling reactions of aryl tosylates with arylboronic acids: vital role of dppf

An air-stable and easy-to-handle nickel precatalyst, (9-phenanthrenyl)Ni(II)(PPh₃)₂Cl, was examined for the cross-coupling reactions of aryl tosylates with arylboronic acids. Under the optimized reaction conditions, the catalytic system tolerates a wide range of activated, neutral and deactivated substrates. The selectivity of this cross-coupling reaction towards aryl tosylates and arylboronic acids has been investigated. It is proposed that ligand 1,1′-bis(diphenylphosphino)ferrocene (dppf) plays a key role in the coupling by enforcing a cis geometry in key intermediates and the active Ni(0) species.     

Use of cheaper metal than Rh, CHCl3-free Pd catalyst, in 1,2-addition of aromatic aldehydes with arylboronic acids

Pd(OAc)₂-(±)-tol-BINAP-catalyzed arylation reaction of aromatic aldehydes with arylboronic acids in the absence of CHCl₃ is described.     

Regioselective arylation of 2′-deoxyribonucleosides on amido or imino sites by copper(II)-mediated direct coupling with arylboronic acids

N¹-Aryl derivatives of 2′-deoxyguanosine (dG) were synthesized by copper(II)-mediated coupling of dG with arylboronic acids. Analogous aryl derivatives of 2′-deoxyinosine (dIn), 2′-deoxyuridine (dU), thymidine (T), 2′-deoxyadenosine (dA), and 2′-deoxycytidine (dC) were also conveniently synthesized by this method. Arylation took place preferentially on the amido functions in dG and dIn and the imino functions in dU or T. Remarkably, the nucleosides themselves served as internal ligands as well as reactants.     

A novel sustainable strategy for the synthesis of phenols by magnetic CuFe2O4-catalyzed oxidative hydroxylation of arylboronic acids under mild conditions in water

A novel sustainable strategy for the synthesis of phenols has been developed using inexpensive, readily available, air-stable, and recyclable CuFe₂O₄ nanoparticles as the catalyst, and the corresponding substituted phenols were obtained in moderate to good yields by oxidative hydroxylation of arylboronic acids in water. Importantly, a ligand or an additive was not necessary. The catalyst was completely recoverable with an external magnet and could be reused six times without significant loss of catalytic activity.     

Microwave-promoted cross-coupling of acid chlorides with arylboronic acids: a convenient method for preparing aromatic ketones

Simple catalytic systems for cross-coupling reactions of acyl chlorides with arylboronic acids under microwave conditions were tested. Microwave irradiation facilitated the reaction course. Mild reaction conditions afford the symmetrical and unsymmetrical aryl ketones in reasonable to high yields within a short time. A wide range of substrates bearing an electron-donating or an electron-withdrawing substituent on aryl ring of acid chloride as well as on boronic acid were examined and high yields of ketones were produced.     

Use of highly reactive, versatile and air-stable palladium-phosphinous acid complex [(t-Bu)2P(OH)]2PdCl2 (POPd) as a catalyst for the optimized Suzuki-Miyaura cross-coupling of less reactive heteroaryl chlorides and arylboronic acids

Using highly reactive air-stable palladium-phosphinous acid complex [(t-Bu)₂P(OH)]₂PdCl₂ (POPd) as a catalyst, synthesis of heteroaryl-aryl cross-coupled products via palladium-catalyzed Suzuki-Miyaura coupling of less reactive substituted 3-chloropyridines with arylboronic acids was achieved in high yields.     

Metal phosphonates containing pyridyl N-oxide groups: Syntheses of Cd{(2-C5H4NO)CH(OH)PO3}(H2O)2 and Zn{(4-C5H4NO)CH(OH)PO3} with chain and layer structures

This paper reports the syntheses and characterization of two phosphonate compounds Cd{(2-C₅H₄NO)CH(OH)PO₃}(H₂O)₂ (1) and Zn{(4-C₅H₄NO)CH(OH)PO₃} (2) based on hydroxy(2-pyridyl N-oxide)methylphosphonic and hydroxy(4-pyridyl N-oxide)methylphosphonic acids. Compound 1 has a chain structure in which dimers of edge-shared {CdO₆} octahedra are linked by {CPO₃} tetrahedra through corner-sharing. The pyridyl rings reside on the two sides of the inorganic chain. Compound 2 has a layer structure where the inorganic chains made up of corner-sharing {ZnO₄} and {CPO₃} tetrahedra are covalently connected by pyridyl N-oxide groups. Crystal data for 1: triclinic, space group , a=6.834(1) Å, b=7.539(1) Å, c=10.595(2) Å, α=84.628(3)°, β=74.975(4)°, γ=69.953(4)°. For 2: triclinic, space group , a=5.219(1) Å, b=8.808(2) Å, c=9.270(2) Å, α=105.618(5)°, β=95.179(4)°, γ=94.699(4)°.     

Pd(II)-catalyzed annulation of N-benzyl-N-aroylmethyl-2-alkynamides with arylboronic acids: an efficient synthesis of highly substituted α-alkylidene-β-hydroxy-γ-lactams

A simple palladium(II)-catalyzed intramolecular addition of vinylpalladium species to ketones initiated by the carbopalladation of alkynamides under mild conditions without a Pd(II)/Pd(0) redox system was developed. This cascade reaction provides a new approach for the synthesis of highly substituted α-alkylidene-β-hydroxy-γ-lactams.     

Synthesis and structure of two lanthanide complexes with isonicotinic acid N-oxide (HL): [Ln(L)2(H2O)4]n·(NO3)n·n(H2O) (Ln = Sm or Tb)

Two new lanthanide complexes of isonicotinic acid N-oxide (HL), namely [Ln(L)₂(H₂O)₄]_n·(NO₃)_n·n(H₂O) for Ln = Sm or Tb, have been synthesized and characterized by spectroscopic and crystallographic methods. IR spectra suggest that isonicotinic acid N-oxide acts as a O,O′-bidentate ligand, the N-oxide group as well as the nitrate group are not involved in coordination. Single crystal analyses have shown that both complexes are isomorphous, where the Ln(III) centers are eight coordinated by four O atoms of four water ligands and other four O atoms of two isonicotinic acid N-oxide ligands. The carboxylate groups are only involved in the bidentate syn–syn bridging mode into infinite chains. Hydrogen bonds between aqua ligands, lattice molecules, nitrate and N-oxide groups are formed giving a three-dimensional network.     

An alternate approach to quinoline architecture via Baylis-Hillman chemistry: SnCl2-mediated tandem reaction toward synthesis of 4-(substituted vinyl)-quinolines

An alternate approach to densely substituted quinolines from the products of S_N2 nucleophilic substitution reaction between the acetyl derivatives of the Baylis-Hillman adducts obtained from 2-nitrobenzaldehydes and the carbonyl group containing carbon nucleophiles is described. Treatment of these compounds with SnCl₂, triggers a tandem reaction wherein reduction of the nitro group is followed by a remarkably regioselective intramolecular cyclization and subsequent dehydrogenation to afford 4-(substituted vinyl)-quinolines.     

I2/K2CO3-promoted ring-opening/cyclization/rearrangement/aromatization sequence: A powerful strategy for the synthesis of polysubstituted furans

An efficient and straightforward synthetic method has been developed for the preparation of 4-cyanofuran-3-carboxylate derivatives via iodine/potassium carbonate-promoted ring-opening/cyclization/rearrangement domino reaction of 1-cyanocyclopropane-1-carboxylates, which are a wide range of structurally interesting and pharmacologically significant compounds.     

Dimethylaluminum methide complex Tf2CHAlMe2: an effective catalyst for Diels-Alder reaction of α,β-unsaturated lactone derivatives with cyclopentadiene

Lewis acid derived by mixing Tf₂CH₂ and Me₃Al was found to be an effective catalyst system for the catalytic DA reaction of less reactive α,β-unsaturated lactone derivative with cyclopentadiene (CP). In this catalyst system, Tf₂CHAlMe₂ is an active species and an excess amount of Me₃Al plays an important role to lower the catalyst loading. Substituent effect of the lactone framework on π-facial selectivity was also examined. In the reactions of both γ-substituted 5-membered lactone derivatives and γ- or δ-methylated 6-membered lactone derivatives with CP, selective attack on the anti face of γ- or δ-substituent was observed. On the other hand, in the cases of γ- or ?-methylated 7-membered lactone derivatives, CP favorably attacked on the syn face.     

Bi4O5Br2光催化剂的制备及可见光降解卡马西平的活性研究

采用水解法合成了Bi_4O_5Br_2光催化剂,并通过XRD、SEM和DRS等手段对催化剂的结构、形貌和光吸收性质进行了表征。结果表明,催化剂呈不规则片状结构,其带隙能为2.1eV,价带电位E_(VB)和导带电位E_(CB)分别为2.61和0.51 eV。基于反应原理和表征结果,提出了催化剂形成机理。在可见光照射下,Bi_4O_5Br_2对卡马西平表现出高效的光催化氧化活性,光照120min后,卡马西平的降解率超过90%,反应动力学速率常数k达到0.018min~(-1)。捕获剂实验结果表明卡马西平降解过程中的主要活性物质是光生空穴(h~+)和超氧自由基阴离子(·O~-_2)。致畸作用实验结果表明,可见光照射120min后,卡马西平溶液基本上没有污染。此外,Bi_4O_5Br_2光催化剂在光催化降解卡马西平过程中表现出较高的化学稳定性和可重复性,表明其具有实际应用的潜力。     

A highly selective magnetic sensor with functionalized Fe/Fe3O4 nanoparticles for detection of Pb2+

A magnetic sensor for detection of Pb~(2+) has been developed based on Fe/Fe_3O_4 nanoparticles modified by3-(3,4-dihydroxyphenyl)propionic acid(DHCA). The carboxyl groups of DHCA have a strong affinity to coordination behavior of Pb~(2+) thus inducing the transformation of Fe/Fe_3O_4 nanoparticles from a dispersed to an aggregated state with a corresponding decrease, then increase in transverse relaxation time(T_2) of the surrounding water protons. Upon addition of the different concentrations of Pb~(2+) to an aq. solution of DHCA functionalized Fe/Fe_3O_4 nanoparticles(DHCA-Fe/Fe_3O_4 NPs)([Fe] = 90 mmol/L), the change of T_2 values display a good linear relationship with the concentration of Pb~(2+) from 40 μmol/L to 100 μmol/L and from 130 μmol/L to 200 μmol/L, respectively. Owing to the especially strong interaction between DHCA and Pb~(2+), DHCA-Fe/Fe_3O_4 NPs exhibited a high selectivity over other metal ions.     

Environmentally benign oxidation reaction of aldehydes to their corresponding carboxylic acids using Pd/C with NaBH4 and KOH

Pd/C catalyst in aqueous methanol with sodium borohydride and potassium hydroxide under the air efficiently oxidized aldehydes to their corresponding carboxylic acids at room temperature. The utilization of room temperature reaction, aqueous methanol solvent, and the open-air conditions make this manipulation very interesting for economic and environmental perspectives.