87170-83-0Relevant articles and documents
Platinum Assisted Tandem P–C Bond Cleavage and P–N Bond Formation in Amide Functionalized Bisphosphine o-Ph2PC6H4C(O)N(H)C6H4PPh2-o: Synthesis, Mechanistic, and Catalytic Studies
Balakrishna, Maravanji S.,Kunchur, Harish S.
supporting information, (2022/01/19)
The reactions of amide functionalized bisphosphine o-Ph2PC6H4C(O)N(H)C6H4PPh2-o (1) with platinum salts are described. Treatment of 1 with [Pt(COD)Cl2] yielded a chelate complex, [PtCl2{o-Ph2PC6H4C(O)N(H)C6H4PPh2-o}κ2-P,P] (2), which on subsequent treatment with LiHMDS formed a novel 1,2-azaphospholene-phosphine complex [Pt(C6H5)Cl{o-C6H4{C(O)N(o-PPh2(C6H4))P(Ph)}}κ2-P,P] (3) involving a tandem P–C bond cleavage and P–N bond formation. The same complex 3 on passing dry HCl gas afforded the dichloro complex [PtCl2{o-C6H4{C(O)N(o-PPh2(C6H4))P(Ph)}}κ2-P,P] (5). Complex 2 upon refluxing in toluene or treatment of 1 with [Pt(COD)Cl2] in the presence of a base at room temperature resulted in the pincer complex [PtCl{o-Ph2PC6H4C(O)N(C6H4PPh2-o)}κ3-P,N,P] (4). Reaction of 1 with [Pt(COD)ClMe] at room temperature also afforded the pincer complex [PtMe{o-Ph2PC6H4C(O)N(C6H4PPh2-o)}κ3-P,N,P] (6). Mechanistic studies on 1,2-azaphospholene formation showed the reductive elimination of LiCl to form a phosphonium salt that readily adds one of the P–C bonds oxidatively to the in situ generated Pt0 species to form a chelate complex 3. The analogous palladium complex [PdCl2{o-C6H4{C(O)N(o-PPh2(C6H4))P(Ph)}}κ2-P,P] (7) showed excellent catalytic activity toward N-alkylation of amines with alcohols with a very low catalyst loading (0.05 mol %), and the methodology is very efficient toward the gram-scale synthesis of many N-alkylated amines.
Systematic research of H2dedpa derivatives as potent inhibitors of New Delhi Metallo-β-lactamase-1
Bai, Meng-Meng,Cui, De-Yun,Han, Jiang-Xue,Kong, Hong-Tao,Liu, Yi-Shuang,Shen, Bo-Yuan,Wang, Cong-Cong,Xiao, Chun-Ling,Yan, Da-Chao,Yang, Yi,Zhang, En
, (2020/06/01)
New Delhi Metallo-β-lactamase-1 (NDM-1), a Zn (II)-dependent enzyme, can catalyze the hydrolysis of almost all β-lactam antibiotics including carbapenems, resulting in bacterial antibiotic resistance, which threatens public health globally. Based on our finding that H2dedpa is as an efficient NDM-1 inhibitor, a series of H2dedpa derivatives was systematically prepared. These compounds exhibited significant activity against NDM-1, with IC50 values 0.06–0.94 μM. In vitro, compounds 6k and 6n could restore the activity of meropenem against Klebsiella pneumoniae, Escherichia coli and Proteus mirabilis possessing either NDM or IMP. In particular, the activity of meropenem against E. coli producing NDM-4 could be improved up to 5333 times when these two compounds were used. Time–kill cell-based assays showed that 99.9% of P. mirabilis were killed when treated with meropenem in combination with compound 6k or 6n. Furthermore, compounds 6k and 6n were nonhemolytic (HC50 > 1280 μg/mL) and showed low toxicity toward mammalian (HeLa) cells. Mechanistic studies indicated that compounds 6k and 6n inhibit NDM-1 by chelating the Zn2+ ion of the enzyme.
A new macrocyclic heterobinuclear Cu(II)-Zn(II) complex: synthesis, crystal structure, phosphate hydrolysis, and DNA binding studies
Kou, Huizhi,Wang, Yang,Ding, Peipei,Li, Jianfen,Shi, Baoxian
, p. 1683 - 1696 (2019/05/22)
A new macrocyclic heterobinuclear Cu(II)-Zn(II) complex was synthesized and characterized by elemental analysis, FT-IR, ES-MS, and single-crystal X-ray diffraction. Five-coordinate geometry for the new complex is proposed. The copper…zinc distance bridged by two phenolic oxygens and a acetate ligand is 2.9508 ?. The phosphate ester hydrolysis activity and the DNA binding ability of the complex were studied. The results showed that the present complex has an efficient catalytic activity of phosphoester bond cleavage. The catalytic rate constant kcat for the hydrolysis of 4-nitrophenyl phosphate disodium salt hexahydrate (pNPP) by the synthesized complex is 2.69 × 10?4 s?1 and 105 times faster than the spontaneous hydrolysis of the phosphate monoester. The complex shows a good binding ability to calf thymus (CT-DNA) and the corresponding binding constant is 1.9 × 105 M?1. The linear Stern-Volmer quenching constant obtained by the fluorescent spectroscopic is 6.3 × 104 M?1.
Synthesis of heterobinuclear Cu(Ⅱ)-Ni(Ⅱ) complex: Structure, CT-DNA interaction, hydrolytic function and antibacterial studies
Ding, Peipei,Wang, Yang,Kou, Huizhi,Li, Jianfen,Shi, Baoxian
, p. 836 - 843 (2019/07/12)
A new benzyls pendant-armed macrobicyclic heterbinuclear Cu(Ⅱ)-Ni(Ⅱ) complex has been obtained by template-directed synthesis and characterized by elemental analysis, IR spectra, electrospray mass spectra, and single crystal X-ray diffraction. The complex was bridged by two phenolic oxygens and an acetate radical, with the Cu(Ⅱ)-Ni(Ⅱ) distance of 2.9292(8) ?. The hydrolytic function, CT-DNA binding and antibacterial properties were also studied. The initial rate values for the hydrolysis of 4-nitophenylphosphate to 4-nitrophenolate by the Cu(Ⅱ)-Ni(Ⅱ) complex was 1.33 × 10?5 s?1, and 104 times faster than that the spontaneous hydrolysis of the phosphate monoester. The complex shows a better binding property to CT-DNA and the intrinsic binding constant is 1.29 × 105 M?1. The Stern-Volmer constant is 1.25 × 105 M?1. The viscosity increased obviously with the increase of complex concentration, the results showed that the complex bind to DNA through intercalation mode, which was in accordance with the absorption and emission spectral studies. The antibacterial activities against E.coli was also investigated using the Gentamycinas reference system.
Manganese-Catalyzed Transfer Hydrogenation of Aldimines
Wei, Duo,Bruneau-Voisine, Antoine,Dubois, Maxime,Bastin, Stéphanie,Sortais, Jean-Baptiste
, p. 5256 - 5259 (2019/04/17)
The reduction of imines to amines via transfer hydrogenation was achieved promoted by phosphine-free manganese(I) catalyst. Using isopropanol as reductant, in the presence of tBuOK (4 mol %) and manganese complex [Mn(CO)3Br(κ2N,N-PyCH2NH2)] (2 mol %), a large variety of aldimines (30 examples) were typically reduced in 3 hours at 80 °C with good to excellent yield.
Design, synthesis and evaluation against Mycobacterium tuberculosis of azole piperazine derivatives as dicyclotyrosine (cYY) mimics
El-wahab, Hend A.A. Abd,Accietto, Mauro,Marino, Leonardo B.,McLean, Kirsty J.,Levy, Colin W.,Abdel-Rahman, Hamdy M.,El-Gendy, Mahmoud A.,Munro, Andrew W.,Aboraia, Ahmed S.,Simons, Claire
, p. 161 - 176 (2017/11/29)
Three series of azole piperazine derivatives that mimic dicyclotyrosine (cYY), the natural substrate of the essential Mycobacterium tuberculosis cytochrome P450 CYP121A1, were prepared and evaluated for binding affinity and inhibitory activity (MIC) against M. tuberculosis. Series A replaces one phenol group of cYY with a C3-imidazole moiety, series B includes a keto group on the hydrocarbon chain preceding the series A imidazole, whilst series C explores replacing the keto group of the piperidone ring of cYY with a CH2-imidazole or CH2-triazole moiety to enhance binding interaction with the heme of CYP121A1. The series displayed moderate to weak type II binding affinity for CYP121A1, with the exception of series B 10a, which displayed mixed type I binding. Of the three series, series C imidazole derivatives showed the best, although modest, inhibitory activity against M. tuberculosis (17d MIC = 12.5 μg/mL, 17a 50 μg/mL). Crystal structures were determined for CYP121A1 bound to series A compounds 6a and 6b that show the imidazole groups positioned directly above the haem iron with binding between the haem iron and imidazole nitrogen of both compounds at a distance of 2.2 ?. A model generated from a 1.5 ? crystal structure of CYP121A1 in complex with compound 10a showed different binding modes in agreement with the heterogeneous binding observed. Although the crystal structures of 6a and 6b would indicate binding with CYP121A1, the binding assays themselves did not allow confirmation of CYP121A1 as the target.
Manganese catalyzed reductive amination of aldehydes using hydrogen as a reductant
Wei, Duo,Bruneau-Voisine, Antoine,Valyaev, Dmitry A.,Lugan, No?l,Sortais, Jean-Baptiste
supporting information, p. 4302 - 4305 (2018/05/03)
A one-pot two-step procedure was developed for the alkylation of amines via reductive amination of aldehydes using molecular dihydrogen as a reductant in the presence of a manganese pyridinyl-phosphine complex as a pre-catalyst. After the initial condensation step, the reduction of imines formed in situ is performed under mild conditions (50-100 °C) with 2 mol% of catalyst and 5 mol% of tBuOK under 50 bar of hydrogen. Excellent yields (>90%) were obtained for a large combination of aldehydes and amines (40 examples), including aliphatic aldehydes and amino-alcohols.
Preparation method of N,N-dibenzyl ethylenediamine diacetate
-
Page/Page column 8-10, (2018/10/19)
The invention discloses a preparation method of N,N-dibenzyl ethylenediamine diacetate. The method comprises the following steps: S1, adding 50 parts by weight of diacetyl dibenzyl ethylenediamine material into a three-necked bottle, and adding 80-120 parts by weight of concentrated hydrochloric acid into the three-necked bottle to obtain 36.0-37.5 parts by weight of a compound B; S2, adding 200 parts by weight of water into the compound B obtained in the step S1 for fully dissolving, and dropwise adding a sodium hydroxide solution to adjust the pH value to 8-9; then, adding toluene for extracting for a plurality of times, and carrying out layered treatment to obtain an organic phase of a mixture of a compound C and the toluene; S3, adding the organic phase of the mixture of the compound Cand toluene into the three-necked bottle and distilling under the reduced pressure until no fraction is obtained, then adding ethyl acetate for dissolving, heating up to 60 DEG C, then dropwise adding 20 parts by weight of glacial acetic acid, and drying to obtain 47.0-49.0 parts by weight of dibenzyl ethylenediamine diacetate finally. The preparation method provided by the invention improves thereaction safety and reduces the reaction cost; furthermore, the yield of the dibenzyl ethylenediamine diacetate is also increased to 93% or above.
METAL CHELATORS FOR IMAGING, THERAPEUTICS, AND BIOANALYSIS
-
Paragraph 0154, (2018/09/26)
A variety of compounds are provided capable of chelating a metal, in particular a lanthanide such as Eu(III) and Tb(III). Luminescent complexes of the compound and a metal ion are also provided, in particular luminescent metal complexes are provided containing a lanthanide such as Eu(III) or Tb(III) and a compound described herein. In some aspects, the luminescent complexes are capable of exhibiting bright emissions with high quantum yields. Methods of making the compound are provided. Methods of using the compounds and luminescent complexes are also provided, for example for imaging and therapeutic applications.
One-pot synthesis of imidazolinium salts via the ring opening of tetrahydrofuran
Huang, Yong-Qing,Zhao, Yue,Wang, Peng,Okamura, Taka-Aki,Laforteza, Brian N.,Lu, Yi,Sun, Wei-Yin,Yu, Jin-Quan
supporting information, p. 12430 - 12433 (2017/10/06)
A new one-pot synthesis of C2-hydroxypropyl-substituted imidazolinium salts via the ring opening of tetrahydrofuran (THF) with N,N′-disubstituted diamines has been developed. Preliminary studies of the reaction mechanism suggest the CO2-promoted oxidative ring opening of THF followed by Hg(ii)-mediated oxidation of an imidazolidine intermediate. These novel C2-substituted imidazolinium salts have shown to be active catalysts for the aza-Diels-Alder reactions.
