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Transition metal- and base-free synthesis of N-substituted indoles from primary amines and MBH acetate of cyclohexenone is developed.

A series of

Chemodivergent reactions of 2,2-dimethoxyacetaldehyde and anilines were described, which were established on the basis of either a C C bond cleavage or a rearrangement process of a reaction intermediate. These reactions proceeded in a condition-determined manner with good functional group tolerance. In the first model, 2,2-dimethoxyacetaldehyde reacted with aniline to form a new C N bond, in the presence of O2, via a C C bond cleavage reaction. However, in the second model, by performing the reaction in the absence of O2, Heyns rearrangement occurred and generated a new C O bond to form methyl phenylglycinate. Such condition-determined reactions not only offered the new way for value-added conversion of biomass-derived platform molecule, 2, 2-dimethoxyacetaldehyde, but also provided efficient methods for the synthesis of N-arylformamides and methyl phenylglycinates.

N-Aryl/alkyl 3-carbonylpyrroles are ubiquitous in compounds of biological and material significance, whereas their synthesis traditionally requires a multistep protocol. Herein a kalinite catalyzed direct synthesis of N-substituted 3-carbonylpyrroles from a 2,2-dimethoxyacetaldehyde derived Morita–Baylis–Hillman acetate and a primary amine in ethanol is developed. This reaction is scalable and also applicable to the synthesis of JMH-030, JMC-2004 and other bioactive compounds.

Gold–palladium (Au–Pd) bimetallic nanoparticle (NP) catalysts supported on MIL-101(Cr) with Au : Pd mole ratios ranging from 1 : 3 to 3 : 1 were prepared through coimpregnation and H2 reduction. Au–Pd NPs were homogeneously distributed on the MIL-101(Cr) with mean particle sizes of 5.6 nm. EDS and XPS analyses showed that bimetallic Au–Pd alloys were formed in the Au(2)Pd(1)/MIL-101(Cr). The catalytic performance of the catalysts was explored in the selective 1,3-butadiene hydrogenation at 30–80 °C on a continuous fixed bed flow quartz reactor. The bimetallic Au–Pd alloy particles stabilized by MIL-101(Cr) presented improved catalytic performance. The as-synthesized bimetallic Au(2)Pd(1)/MIL-101(Cr) with 2 : 1 Au : Pd mole ratio showed the best balance between the activity and butene selectivity in the selective 1,3-butadiene hydrogenation. The Au–Pd bimetallic-supported catalysts can be reused in at least three runs. The work affords a reference on the utilization of a MOF and alloy nanoparticles to develop high-efficiency catalysts.

A series of novel pyrano[2,3-c]pyrazoles were synthesized and screened for their potential to inhibit kinases and exhibit anti-cancer activity against primary patient derived glioblastoma 2D cells and 3D neurospheres. A collection of 10 compounds were evaluated against glioma cell lines, with compound 4j exhibiting promising glioma growth inhibitory properties. Compound 4j was screened against 139 purified kinases and exhibited low micromolar activity against kinase AKT2/PKBβ. AKT signalling is one of the main oncogenic pathways in glioma and is often targeted for novel therapeutics. Indeed AKT2 levels correlated with glioma malignancy and poorer patient survival. Compound 4j inhibited the 3D neurosphere formation in primary patient derived glioma stem cells and exhibited potent EC50 against glioblastoma cell lines. Herein we establish a novel biochemical kinase inhibitory function for a pyrano[2,3-c]pyrazole derivative and further report its anti-glioma activity in vitro for the first time.

Three bimetallic Cu&ndash, Ni nanoparticle-supported catalysts were synthesized by co-immobilization followed by H2 reduction. A chromium(III) terephthalate metal organic framework (MIL-101), titanium dioxide (TiO2), and carbon (C) with different properties (acidity and Brunauer&ndash, Emmett&ndash, Teller surface area) were selected as supports for studying the effect of the support nature on the catalytic activity and selectivity in the oxidation of benzyl alcohol. The physicochemical properties of the Cu&ndash, Ni-supported catalysts were characterized by XRD, NH3-TPD, nitrogen adsorption/desorption, TEM, EDS, XPS, and ICP-OES. Bimetallic Cu&ndash, Ni nanoparticles were highly dispersed on the support. The catalytic activities of CuNi/MIL-101, CuNi/TiO2, and CuNi/C were tested in the selective oxidation of benzyl alcohol to benzaldehyde in the presence of molecular oxygen under mild reaction conditions. The highest benzaldehyde yields were achieved with CuNi/TiO2, CuNi/MIL-101, and CuNi/C catalysts at 100 &deg, C within 4 h under 5, 3, and 3 bar of O2, respectively. The bimetallic Cu&ndash, Ni-supported catalysts possessed two types of catalytic active sites: acid sites and bimetallic Cu&ndash, Ni nanoparticles. The CuNi/MIL-101 catalyst possessed a high number of acid sites and exhibited high yield during selective benzyl alcohol oxidation to benzaldehyde. Importantly, the catalysts exhibited a high functional group (electron-donating and electron-withdrawing groups) tolerance. Cu&ndash, Ni-supported catalysts with an Cu:Ni mole ratio of 1:1 exhibited the highest yield of 47% for the selective oxidation of benzyl alcohol to benzaldehyde. Reusability and leaching experiment results exhibited that CuNi/MIL-101 showed better stability than CuNi/TiO2 and CuNi/C catalysts due to the large porous cavities of MIL-101 support, these cavities can be used to trap bimetallic Cu&ndash, Ni nanoparticles and inhibit nanoparticle leaching.