RESUMO
The mol-ecule of the title NCNHCS pincer N-heterocyclic carbene palladium(II) complex, [PdBr(C21H25N3S)]Br, exhibits a slightly distorted square-planar coordination at the palladium(II) atom, with the five-membered chelate ring nearly planar. The six-membered chelate ring adopts an envelope conformation. Upon chelation, the sulfur atom becomes a stereogenic centre with an RS configuration induced by the chiral carbon of the precursor imidazolium salt. There are intra-molecular C-Hâ¯Br-Pd hydrogen bonds in the structure. The two inter-stitial Br atoms, as the counter-anion of the structure, are both located on crystallographic twofold axes and are connected to the complex cations via C-H⯷Br hydrogen bonds.
RESUMO
A one-pot strategy for deoxygenative alkylation of alcohols with quinoxalin-2(1H)-ones was developed by using xanthate salts as alcohol-activating groups for radical generation in the presence of tricyclohexylphosphine under visible-light-promoted conditions. The remarkable features of this reaction include a broad substrate scope, excellent functional group tolerance, mild conditions, and simple operation. Moreover, the synthetic utility of this reaction was validated by the success of two-step one-pot reactions, scale-up synthesis, and chemoselective radical monodeoxygenation of diols.
RESUMO
A photochemical approach toward RCOCF2-substituted pyrrolo[1,2-a]indolediones was developed by the radical cascade difluoroalkylation/cyclization reaction of unactivated 1-acryloyl-2-cyanoindoles with ethyl iododifluoroacetate or iododifluoramides under visible-light irradiation. This transition-metal- and photosensitizer-free protocol afforded diverse difluoroalkylated pyrrolo[1,2-a]indolediones in moderate to good yields under mild reaction conditions. Most appealingly, the reaction can proceed smoothly under sunlight irradiation, which opens a new avenue toward difluoroalkylated pyrrolo[1,2-a]indolediones.
RESUMO
An ethyl 3-aminobenzo[b]thiophene-2-carboxylate derived ratiometric Schiff base fluorescent sensor R was devised and synthesized. R exhibited a highly sensitive and selective ratiometric response to In3+ in DMF/H2O tris buffer solution. R exhibited a colorimetric/fluorescent dual-channel response to In3+. More importantly, R can distinguish In3+ from Ga3+ and Al3+ in less than 5 min. R exhibited a good linear correlation with the concentration of In3+ in the 5-25 µM range and the limit of detection for In3+ was found to be 8.36 × 10-9 M. According to the job`s plot and MS spectra, R formed a complex with In3+ at 1:2 with a complexation constant of 8.24 × 109 M2. Based on Gaussian theory calculations, the response mechanism of R to In3+ can be explained by photo-induced electron transfer (PET) and intramolecular charge transfer (ICT) mechanisms. In addition, R can be used for the detection of indium in tap water with satisfactory recoveries. Meanwhile, R displayed a linear relationship to micromolar concentrations (0-50 µM) of Pb2+ and recognized Pb2+ in a ratiometric response with a detection limit of 8.3 × 10-9 M.
RESUMO
A photoredox-catalyzed intermolecular tandem sulfonamination/cyclization of enaminones was realized by using N-aminopyridinium salts as the sulfonaminated reagents without transition-metal catalysts or bases. The reaction exhibits a broad scope and good functional group tolerance, good yields, and regioselectivity. Preliminary mechanistic studies support the radical property of the reaction and the involvement of N-centered radical intermediates.
RESUMO
An effective method for accessing diverse difluoroalkylated pyrrolo[1,2-a]indolediones via visible-light-induced PhI(OAc)2-promoted cascade difluoroalkylation/cyclization reaction under mild conditions has been established. This method is noteworthy for its use of DMSO-H2O as a green medium at room temperature and avoidance of photocatalysts. The reactions are straightforward to execute and convenient to expand on, provide good to excellent yields, and have good functional group tolerance.
RESUMO
A practical and metal-free approach for the regioselective selenation of chromones employing Selectfluor reagent under mild conditions is described. The developed method is suitable for a wide substrate scope and affords 3-selenylated chromones in good to excellent yield with high selectivity. An ionic mechanism is proposed for this transformation. Furthermore, the application of potassium thiocyanate with enaminones for the synthesis of thiocyano chromones in this transformation is also successful.
RESUMO
A convenient and efficient visible-light-induced method has been developed for the construction of sulfonated and selenylated indolo[1,2-a]quinolines through sulfonyl or selenyl radical-initiated tandem cyclization of unactivated alkynes with sodium sulfinates or diaryl diselenides under mild conditions. This protocol, which simply utilizes visible light as the safe and eco-friendly energy source and an inexpensive and nontoxic organic dye as a photocatalyst without the aid of an external photocatalyst, provides various sulfonyl- and selenyl-containing indolo[1,2-a]quinolines in moderate to good yields.
RESUMO
A mild and efficient transition-metal-free radical difluorobenzylation/cyclization of unactivated alkenes toward the synthesis of difluorobenzylated polycyclic quinazolinone derivatives with easily accessible α,α-difluoroarylacetic acids has been developed. This transformation has the advantages of wide functional group compatibility, a broad substrate scope, and operational simplicity. This methodology provided a highly attractive access to pharmaceutically valuable ArCF2-containing polycyclic quinazolinones.
Assuntos
Alcenos , Elementos de Transição , Ciclização , Quinazolinonas , Estrutura Molecular , Radicais LivresRESUMO
A practical synthetic route to construct a variety of 3-benzyl spiro[4,5]trienones was developed via transition-metal Cu/Ag-catalyzed oxidative ipso-annulation of activated alkynes with unactivated toluenes using TBPB as an oxidant under microwave irradiation. This method allows the formation of two carbon-carbon bonds and one carbon-oxygen bond in a single reaction through a sequence of C-H oxidative coupling, ipso-carbocyclization and dearomatization. The advantages of this protocol are its operational simplicity and broad substrate scope, and the ability to afford the desired products in moderate to good yields.
RESUMO
A silver-catalyzed efficient and direct C-H carbamoylation of quinolines with oxamic acids to access carbamoylated quinolines has been developed through oxidative decarboxylation reaction. The reaction proceeds smoothly over a broad range of substrates with excellent functional group tolerance and excellent yields under mild conditions.
RESUMO
A practical and straightforward synthetic route through a fluorination-triggered tandem cyclization of styrene-type carboxylic acids was developed to construct a variety of 4-fluoro-3-aryl-3,4-dihydroisocoumarins and 3-arylisocoumarins under microwave irradiation. This novel protocol features mild reaction conditions and operational simplicity, with good yields.
RESUMO
A novel and convenient palladium-catalyzed direct oxidative amidation of quinoxalin-2(1H)-ones with acetonitrile was developed to synthesize 3-amidated quinoxalin-2(1H)-ones. A series of 3-acetamino quinoxalin-2(1H)-one derivatives were constructed with good to excellent yields. This methodology provided a practical approach to various 3-acetamino quinoxalin-2(1H)-ones from the readily available starting material acetonitrile.
RESUMO
In the title hydrated salt, C19H24N3 (+)·Br(-)·H2O, the values of the N-C bond lengths within the tetra-hydro-pyrimidinium ring indicate delocalization of the N=C double bond. In the cation, the dihedral angle formed by the pyridine and benzene rings is 14.97â (12)°. In the crystal, ions and water mol-ecules are linked by O-Hâ¯Br, O-Hâ¯N, C-Hâ¯Br and C-Hâ¯O hydrogen bonds into chains running parallel to the b axis.
RESUMO
Decarboxylative alkylation or acylation reactions of simple pyrimidines have been developed in aqueous media. Using aliphatic carboxylic acids or 2-oxocarboxylic acids and pyrimidines as substrates and silver as the catalyst, the 4-substituted alkyl or acyl pyrimidines were isolated in moderate to good yields.
Assuntos
Ácidos Carboxílicos/química , Pirimidinas/síntese química , Prata/química , Catálise , Descarboxilação , Estrutura Molecular , Pirimidinas/química , Água/químicaRESUMO
A silver-catalyzed efficient and practical synthesis of 3-acyl-4-arylquinolin-2(1H)-ones or 3-acyl-4-aryldihydroquinolin-2(1H)-ones through intermolecular radical addition/cyclization in aqueous solution is reported. This method provides a novel, highly efficient, and straightforward route to substituted quinolin-2-ones or 3,4-dihydroquinolin-2-ones in one step. A possible mechanism for the formation of quinolin-2-ones is proposed.
Assuntos
Quinolonas/química , Quinolonas/síntese química , Prata/química , Ciclização , Estrutura MolecularRESUMO
In the title compound, C30H25N3O3, the central imidazole ring forms dihedral angles of 77.34â (6), 12.56â (6) and 87.04â (6)°, respectively, with the o-nitro-benzene ring and the phenyl substituents in the 5- and 4-positions. The mol-ecular conformation is stabilized by weak intra-molecular C-Hâ¯π inter-actions. In the crystal, mol-ecules are linked by O-Hâ¯N hydrogen bonds, forming chains running parallel to the b-axis direction.
RESUMO
A silver-catalyzed tandem decarboxylative radical addition/cyclization of N-arylcinnamamides with aliphatic carboxylic acids is reported. This method affords a novel and straightforward route to various 3,4-disubstituted dihydroquinolin-2(1H)-ones in aqueous solution.
Assuntos
Quinolonas/síntese química , Prata/química , Ácidos Carboxílicos/química , Catálise , Cinamatos/química , Cristalografia por Raios X , Ciclização , Radicais Livres/síntese química , Radicais Livres/química , Modelos Moleculares , Estrutura Molecular , Quinolonas/químicaRESUMO
In the title compound, C34H28N2S2, the central imidazole ring (r.m.s. deviation = 0.0015â Å) forms dihedral angles of 55.7â (3), 17.94â (11) and 86.27â (11)°, respectively, with the mean planes of the attached thienyl and two phenyl substituents. The thienyl ring shows ring-flip disorder [occupancy ratio = 0.647â (2):0.353â (2)]. The chiral centre maintains the S configuration of the l-phenyl-alaninol starting material. Intra- and inter-molecular C-Hâ¯S hydrogen bonds involving the disordered thienyl ring are observed.
RESUMO
In the title methyl-ene-bridged di(tetra-hydro-pyrimidinium) salt, C33H50N4 (2+)·2Br(-)·C2H5OH·H2O, the two tetra-hydro-pyrimidinium rings have envelope conformations with the central CH2 C atom as the flap. Their mean planes are inclined to one another by 73.31â (13)° and the attached benzene rings are inclined to one another by 67.39â (15)°. The methylene-C-N bond lengths in the tetra-hydro-pyrimidinium rings are 1.314â (3) and 1.304â (3)â Å, values typical for C=N double bonds. The distances between the methyl-ene-bridge C atom and the linked tetra-hydro-pyrimidinium N atom are 1.457â (3) and 1.465â (3)â Å, values typical for C-N single bonds. The mol-ecules co-crystallized with H2O and EtOH mol-ecules from the solvent. In the crystal, there is a zigzag chain along [010] of water mol-ecules linked by one of the Br(-) anions via O-Hâ¯Br hydrogen bonds. The second Br(-) anion is hydrogen bonded (O-Hâ¯Br) to the ethanol solvent mol-ecule. There are also a number of C-Hâ¯Br and C-Hâ¯O hydrogen bonds present, leading to the formation of a two-dimensional network lying parallel to the bc plane.