Chiral transition-metal complexes as Brønsted-acid catalysts for the asymmetric Friedel-Crafts hydroxyalkylation of indoles.

The Friedel-Crafts reaction between 3,3,3-trifluoropyruvates and indoles is efficiently catalysed by the iridium complex [(η5-C 5Me5)Ir{(R)-Prophos}(H2O)][SbF 6]2 (1) with up to 84% ee. Experimental data and theoretical calculations support a mechanism involving the Brønsted-acid activation of the pyruvate carbonyl by the protons of the coordinated water molecule in 1. Water is not dissociated during the process and, therefore, the catalytic reaction occurs with no direct interaction between the substrates and the metal. This journal is © the Partner Organisations 2014.The authors acknowledge the Ministerio de Economía y Competitividad (MINECO, Grants CTQ2006-03030/BQU, CTQ2009-10303/BQU, CTQ2011-27033 and Consolider Ingenio 2010 CSD2006-003), Gobierno de Aragón (Grupo Consolidado: Catálisis Homogénea Enantioselectiva), Generalitat de Catalunya (2009SGR0259) and the ICIQ foundation for financial support. A. S. and R. R. acknowledge MINECO for predoctoral fellowships. S. D.-G. acknowledges MINECO for a “Torres Quevedo” contract.Peer Reviewe

Rationale for the sluggish oxidative addition of aryl halides to Au(I)

The oxidative addition of Csp2–Br or Csp2–I bonds to gold(I) does not take place even under very favorable intramolecular conditions that could form five- or six-membered gold(III) metallacycles. DFT calculations reveal that although this process could be feasible thermodynamically, it is kinetically very sluggish

De problematiek van de kasgrondteelten: Mogelijke oplossingen aangedragen door ondernemers met substraatbedden in het bijzonder

De kasgrond glastuinbouw ziet zich geconfronteerd met stijgende kosten en een afname van de hoeveelheid toegelaten gewasbeschermingsmiddelen. Het middelenpakket tegen schadelijke bodemschimmels en aaltjes wordt mogelijk verkleind (Spruit e.a. 2008). Op dit moment is grondstomen nog een optie, maar door de sterk toenemende energie- en arbeidskosten wordt grondstomen steeds duurder. In voorgaande gesprekken met ondernemers en betrokkenen blijkt dat een teeltsysteem dat relatief goedkoop, en gemakkelijk in de praktijk is in te passen, de voorkeur heeft. Doelstelling van dit project is daarom het in kaart brengen van problemen met mogelijke oplossingen ten aanzien van bodemproblematiek in kasgrondteelten

A computational study on the intriguing mechanisms of the gas-phase thermal activation of methane by bare [Ni(H)(OH)](+)

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.A detailed computational study on the reaction mechanisms of the thermal activation of methane by the bare complex [Ni(H)(OH)]+ has been conducted. The experimentally observed reaction features, i.e. the ligand exchange Ni(H) → Ni(CH3), the H/D scrambling between the incoming methane and the hydrido ligand of the nickel complex, the spectator-like behavior of the OH ligand, and the relatively moderate reaction efficiency of 6% relative to the collision rate of the ion/molecule reaction, can be explained by considering three competing mechanisms, and a satisfactory agreement between experiment and theory has been found.DFG, EXC 314, Unifying Concepts in Catalysi

Computationally Guided Design of a Readily Assembled Phosphite- Thioether Ligand for a Broad Range of Pd-Catalyzed Asymmetric Allylic Substitutions

A modular approach employing indene as common starting material, has enabled the straightforward preparation in three reaction steps of P-thioether ligands for the Pd-catalyzed asymmetric allylic substitution. The analysis of a starting library of P-thioether ligands based on rational design and theoretical calculations has led to the discovery of an optimized anthracenethiol derivative with excellent behavior in the reaction of choice. Improving most approaches reported to date, this ligand presents a broad substrate and nucleophile scope. Excellent enantioselectivities have been achieved for a range of linear and cyclic allylic substrates using a large number of C-, N-, and O-nucleophiles (40 compounds in total). The species responsible for the catalytic activity have been further investigated by NMR in order to clearly establish the origin of the enantioselectivity. The resulting products have been derivatized by means of ring-closing metathesis or Pauson–Khand reactions to further prove the synthetic versatility of the methodology for preparing enantiopure complex structures

Photolytic activation of late-transition-metal-carbon bonds and their reactivity toward oxygen

The photolytic activation of palladium(II) and platinum(II) complexes [M(BPI)(R)] (R = alkyl, aryl) featuring the 1,3-bis(2-pyridylimino)isoindole (BPI) ligand has been investigated in various solvents. In the absence of oxygen, the formation of chloro complexes [M(BPI)Cl] is observed in chlorinated solvents, most likely due to the photolytic degradation of the solvent and formation of HCl. The reactivity of the complexes toward oxygen has been studied both experimentally and computationally. Excitation by UV irradiation (365 nm) of the metal complexes [Pt(BPI)Me] and [Pd(BPI)Me] leads to distortion of the square-planar coordination geometry in the excited triplet state and a change in the electronic structure of the complexes that allows the interaction with oxygen. TD-DFT computational studies suggest that, in the case of palladium, the Pd(III) superoxide intermediate [Pd(BPI)(κ1-O2)Me] is formed and, in the case of platinum, the Pt(IV) peroxide intermediate [Pt(BPI)(κ2-O2)Me]. For alkyl complexes where metal–carbon bonds are sufficiently weak, the photoactivation leads to the insertion of oxygen into the metal–carbon bond to generate alkylperoxo complexes: for example [Pd(BPI)OOMe], which has been isolated and structurally characterized. For stronger M–C(aryl) bonds, the reaction of [Pt(BPI)Ph] with O2 and light results in a Pt(IV) complex, tentatively assigned as the peroxo complex [Pt(BPI)(κ2-O2)Ph], which in chlorinated solvents reacts further to give [Pt(BPI)Cl2Ph], which has been isolated and characterized by scXRD. In addition to the facilitation of oxygen insertion reactions, UV irradiation can also affect the reactivity of other components in the reaction mixture, such as the solvent or other reaction products, which can result in further reactions. Labeling studies using [Pt(BPI)(CD3)] in chloroform have shown that photolytic reactions with oxygen involve degradation of the solvent

Passive and Active Oxidation of Si(100) by Atomic Oxygen: A Theoretical Study of Possible Reaction Mechanisms

Reaction mechanisms for oxidation of the Si(100) surface by atomic oxygen were studied with high-level quantum mechanical methods in combination with a hybrid QM/MM (Quantum mechanics/Molecular Mechanics) method. Consistent with previous experimental and theoretical results, three structures, “back-bond”, “on-dimer”, and “dimer-bridge”, are found to be the most stable initial surface products for O adsorption (and in the formation of SiO2 films, i.e., passive oxidation). All of these structures have significant diradical character. In particular, the “dimer-bridge” is a singlet diradical. Although the ground state of the separated reactants, O+Si(100), is a triplet, once the O atom makes a chemical bond with the surface, the singlet potential energy surface is the ground state. With mild activation energy, these three surface products can be interconverted, illustrating the possibility of the thermal redistribution among the initial surface products. Two channels for SiO desorption (leading to etching, i.e., active oxidation) have been found, both of which start from the back-bond structure. These are referred to as the silicon-first (SF) and oxygen-first (OF) mechanisms. Both mechanisms require an 89.8 kcal/mol desorption barrier, in good agreement with the experimental estimates of 80−90 kcal/mol. “Secondary etching” channels occurring after initial etching may account for other lower experimental desorption barriers. The calculated 52.2 kcal/mol desorption barrier for one such secondary etching channel suggests that the great variation in reported experimental barriers for active oxidation may be due to these different active oxidation channels