Search results for "Lewis acids"
showing 10 items of 165 documents
Aminosäureester als chirale Hilfsgruppen in Lewis-Säure-katalysierten Umsetzungen elektronenreicher Siloxydiene mit Iminen
1990
ChemInform Abstract: Reversal of Asymmetric Induction in Stereoselective Strecker Synthesis on Galactosyl Amine as the Chiral Matrix.
1989
Abstract The reversal of the direction of asymmetric induction in Lewis acid catalyzed Strecker synthesis using the 2,3,4,6-tetra-O-pivaloyl-β-D-galactopyranosyl amine 1 is described. In isopropanol or tetrahydrofuran 1 had given ( R )-diastereomers of the corresponding α-amino nitriles preferably. However, in chloroform in the presence of heterogeneous zinc chloride the same auxiliary alternatively leads to an excess of the ( S )-diastereomers.
Nickel as a Lewis Base in a T‐Shaped Nickel(0) Germylene Complex Incorporating a Flexible Bis(NHC) Ligand
2018
Flexible, chelating bis(NHC) ligand 2, able to accommodate both cis- and trans-coordination modes, was used to synthesize (2)Ni(η 2 -cod), 3. In reaction with GeCl2, this produced (2)NiGeCl2, 4, featuring a T-shaped Ni(0) and a pyramidal Ge center. Complex 4 could also be prepared from [(2)GeCl]Cl, 5, and Ni(cod)2, in a reaction that formally involved Ni-Ge transmetalation, followed by coordination of the extruded GeCl2 moiety to Ni. A computational analysis showed that 4 possesses considerable multiconfigurational character and the Ni→Ge bond is formed through σ-donation from the Ni 4s, 4p, and 3d orbitals to Ge. (NHC)2Ni(cod) complexes 9 and 10, as well as (NHC)2GeCl2 derivative 11, incor…
The Aluminyl Anion : A New Generation of Aluminium Nucleophile
2020
Trivalent aluminium compounds are well known for their reactivity as Lewis acids/electrophiles, a feature that is exploited in many pharmaceutical, industrial and laboratory-based reactions. Recently, a series of isolable aluminium(I) anions ('aluminyls') have been reported, which offer an alternative to this textbook description: these reagents behave as aluminium nucleophiles. This minireview covers the synthesis, structure and reactivity of aluminyl species reported to date, together with their associated metal complexes. The frontier orbitals of each of these species have been investigated using a common methodology to allow for a like-for-like comparison of their electronic structure a…
Iodine(I) and Silver(I) Complexes of Benzoimidazole and Pyridylcarbazole Derivatives
2021
The synthesis of iodine(I) complexes with either benzoimidazole or carbazole-derived sp 2 N -containing Lewis bases is described, as well as their corresponding silver(I) complexes. The addition of elemental iodine to the linear two-coordinate Ag(I) complexes produces iodine(I) complexes with a three-center four-electron (3c-4e) [N — I — N] + bond. The 1 H and 1 H- 15 N HMBC NMR studies unambiguously confirm the formation of the complexes in all cases via the [N — Ag — N] + → [N — I — N] + cation exchange, with the 15 N NMR chemical shift change between 94 to 111 ppm when compared to the free ligand. The single crystal X-ray crystallographic studies on four I + complexes revealed highly sym…
Acidic Co-Catalysts in Cationic Gold Catalysis.
2016
A systematic study on the effects of Lewis or Bronsted acid co-catalysts in gold-catalyzed reactions was undertaken using representative reactions (O-, N-, and C-nucleophilic additions to alkynes). Through these reactions, it was demonstrated that an acidic co-catalyst can increase the catalyst turnover significantly, enabling practical reaction rates at competitive catalyst loadings (<1 mol %). Further investigation is currently underway to improve the understanding of the subtle principles underlying these experimental observations.
A DFT study of the Diels–Alder reaction between methyl acrolein derivatives and cyclopentadiene. Understanding the effects of Lewis acids catalysts b…
2006
Abstract The effects of Lewis acid catalysts based on sulfur containing boron heterocycles on the Diels–Alder reactions of two methyl acroleins with cyclopentadiene have been studied using DFT methods. These reactions take place along highly asynchronous concerted processes. While the reaction with crotonaldehyde leads to the expected endo adduct, the reaction with methacrolein leads to exo one in agreement with the experiments. The catalytic effect can be explained through the analysis of the electrophilicity index (ω) of the reagents, and the molecular structure of the corresponding transition structures.
AlTf-UVM-7—Highly active catalysts for the synthesis of long chain symmetrical ethers and non-ionic surfactant structures
2010
New Lewis acid AlTf-UVM-7 catalysts with bimodal pore system and different Si to Al ratios were prepared in a two-step synthesis in which triflic acid (Tf) was incorporated into previously synthesized mesoporous aluminum-containing silica. The Al incorporation inside the pore walls was carried out through the Atrane method. The characterization of the resulted catalysts showed that the triflic acid treatment step did not damage the texture or the structure of the catalysts. These materials were used as green catalysts for the etherification of fatty alcohols and the conversion of ethylene glycol (EG) with n-octanol resulting in mixtures of short ethoxylated structures with a large distribut…
Recent Advances in Halogen Bonded Assemblies with Resorcin[4]arenes
2020
Resorcinarenes are cavity-containing compounds when in the crown conformation, from the calixarene family of concave compounds. These easy to synthesize macrocycles can be decorated at the upper rim through the eight hydroxyl groups and/or the 2-position of the aromatic ring. They are good synthons in supramolecular chemistry leading to appealing assemblies such as open-inclusion complexes, capsules and tubes through multiple weak interactions with various guests. Halogen bonding (XB) is a highly directional non-covalent interaction by an electron-deficient halogen atom as a donor that interacts with a Lewis base, the XB acceptor. This tutorial review provides an overview of recent advances…
Predicting the activity of single isolated Lewis acid sites in solid catalysts.
2006
An experimental study of the activity of Ti-, Zr- and Sn-beta catalysts in different types of oxidation reactions is combined with a quantum-chemical analysis of the electronic properties of the active sites and the adsorbed reactants. The differences observed in the catalytic behaviour of the three materials are explained in terms of the molecular orbital distribution of each system. The intrinsic Lewis acid strength of the isolated active site, the degree of back-donation from the catalyst to the empty orbitals of the organic reactant and the net atomic charges on selected atoms are proposed as predictors of reactivity.