Designing systems that merge the advantages of heterogeneous catalysis, enzymology, and molecular catalysis represents next major goal for sustainable chemistry. Cross-linked enzyme crystals display most these essential assets (well-designed mesoporous support, protein selectivity, recognition substrates). Nevertheless, a lack reaction diversity, particularly in field oxidation, remains constraint their increased use field. Here, thanks to design cross-linked artificial nonheme iron...

The dinuclear chiral complex Fe2O(bisPB)4(X)2(ClO4)4 (X = H2O or CH3CN) catalyzes with high efficiency (up to 850 TON) and moderate enantioselectivity (63%) the epoxidation of electron deficient alkenes at 0 °C by a peracid.

MAGIC Mn-salen mETALLOZYME: The design of an original, artificial, inorganic, complex-protein adduct, has led to a better understanding the synergistic effects both partners. exclusive formation sulfoxides by hybrid biocatalyst, as opposed sulfone in case free inorganic complex, highlights modulating role inorganic-complex-binding site protein. Artificial metalloenzymes based on incorporation complexes into human serum albumin display high efficiency and selectivity for sulfoxide production...

The substrate for an artificial iron monooxygenase was selected by using docking calculations. high catalytic efficiency of the reported enzyme sulfide oxidation directly correlated to predicted binding mode in protein cavity, thus illustrating synergetic effect site, scaffold, and site. As a service our authors readers, this journal provides supporting information supplied authors. Such materials are peer reviewed may be re-organized online delivery, but not copy-edited or typeset....

Abstract The principle of enzyme mimics has been raised to its pinnacle by the design hybrids made from inorganic complexes embedded into biomolecules. present review focuses on artificial metalloenzymes for oxidation reactions oxygen transfer reactions, with a special focus proteins anchoring or metal ions via supramolecular interactions. Such are great interest organic synthesis building blocks. In first part, following an overview different enzymes, presents contributions rational...

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Abstract A biomimetic approach based on Rieske dioxygenase mimics has been undertaken, which uses the tetradentate N 2 Py ligand platform that contains two pyridine moieties linked to a 1,2‐diaminoethane or trans ‐1,2‐diaminocyclohexane backbone. Here we report impact of incorporation carboxylic functionalities with catalytic efficiency its Fe II complexes during epoxidation H O as oxidant. Five have characterized in solid state and solution. The X‐ray structure ferrous complex acid shows an...

The structural and electronic properties as well the catalytic activity toward sulfoxidation of two new vanadium complexes have been investigated. They both possess in their coordination sphere alkyl thiolate ligands: a dioxido VV complex [VO2LNS2](HNEt3) (1) (LNS2 = 2,2′-(pyridine-2,6-diyl)bis(1,1′-diphenylethanethiol)) an oxido VIV [VOLN2S2] (2) (LN2S2 2,2′-(2,2′-bipyridine-6,6′-diyl)bis(1,1′-diphenylethanethiol)). X-ray structure 1 has revealed that metal ion is at center distorted...

Triphenylphosphane catalyzes conjugate additions of β-dicarbonyl compounds to π-acceptor olefins and dialkyl azodicarboxylates. Formation quaternary centers at the nucleophiles has been achieved. The catalytic action tris(triphenylphosphane)ruthenium(II) chloride tetrakis(triphenylphosphane)ruthenium(II) hydride is least partially due phosphane ligand.

Activation of a ruthenium complex by its insertion into protein scaffold leads to an efficient non natural transformation alkenes α-hydroxy-β-chloro chlorohydrins.

Von Grund auf neu: Das Substrat einer künstlichen Eisenmonooxygenase wurde mithilfe von Docking-Rechnungen ermittelt. Die hohe katalytische Effizienz des Enzyms in der Sulfidoxidation war direkt mit dem vorhergesagten Modus Substratbindung Proteinhöhle korreliert, was die Synergie Substratbindungszentrum, Proteinstruktur und katalytischem Zentrum veranschaulicht. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are...

Ammonia solutions of solvated electrons may be prepared by electrolyzing the solvent in presence Mg(BF4)2 and Mg++ provided a magnesium anode. The reactions these (−40 °C) with two radical clocks 1-bromo-2-(3-butenyl)benzene 1 1-(allyloxy)-2-bromobenzene 7 (0.007−0.008 M) are examined. Both probes yield very high percentages cyclized products (>97%) when concentration is low (0.028 M). These diminish metallic character solution increased (0.183 M electrons). results strongly contrast those...

Abstract In the mechanism of reaction Grignard reagent formation for alkyl halides (RX), it is generally assumed that radical, formed by electron transfer from metal to this halide, reacts rapidly with paramagnetic MgX • species. The previous comparisons aryl reactivity toward magnesium and their a cathode strongly suggested species are not, halides, compulsory rationalise observed facts. radicals halide would undergo rapid second yield carbanions transformed into RMgX 2 . contrast,...

Artificial enzymes represent an attractive alternative to design abiotic biocatalysis. EcNikA-Ru1, artificial metalloenzyme developed by embedding a ruthenium-based catalyst into the cavity of periplasmic nickel-binding protein NikA, was found efficiently and selectively transform certain alkenes. The objective this study provide rationale on enzymatic function unexpected substrate-dependent chemoselectivity EcNikA-Ru1 thanks dual experimental/computational study. We observed that de novo...

Series of new chiral tricyclic pentacoordinated phosphorus compounds, “triquinphosphoranes” (13−18, 21, 22, and 24), were prepared from enantiopure diamino diols that present a C2 symmetry axis. 31P 13C NMR data are consistent either with low-energy single-step Berry pseudorotation process between the two possible diastereomeric trigonal-bipyramidal structures TBP(RP) TBP(SP) or square-pyramidal structure SP. Triquinphosphoranes reacted borane to give stable monoadducts opposite...

Abstract Performing a heterogeneous catalysis with proteins is still challenge. Herein, we demonstrate the importance of cross‐linked crystals for sulfoxide oxidation by an artificial enzyme. The biohybrid consists insertion iron complex into NikA protein crystal. catalysts displays better efficiency‐with higher reaction kinetics, stability and expand substrate scope compared to its solution counterpart. Designing crystalline enzymes represents good alternative soluble or supported future...

The reaction of the title precursor aryl radical clock 1-bromo-2-(3-butenyl)benzene, 1Br, towards potassium and magnesium in THF was studied presence absence various additives, at ambient low temperatures. additives were cis-dicyclohexano-18-crown-6 or tert-butyl alcohol; first one to render soluble by forming its alkalide, second distinguish carbanionic from cyclization. addition 1Br a stirred suspension pieces yields remarkably amounts products resulting cyclization, contrast reported...