Ligand Influence on Metathesis Activity of Ruthenium Carbene Catalysts: A DFT StudyADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2007
Abstract A survey of the concept of active and inactive ligand conformations in ruthenium alkene carbene complexes of the Grubbs catalyst type is presented. This concept is extended to a variety of anionic ligand atoms. Density functional theory calculations at the B3LYP/LACV3P**+//B3LYP/LACVP* level of theory were performed on the precatalyst, 14 valence-electron intermediate, alkene carbene conformers and ruthena(IV)cyclobutane model intermediates for several ligands, such as methoxide, methanethiolate, fluoride, mesylate, water, and ammonia. The rule of the superiority of metathesis catalysts with small and electron-withdrawing halogens does not apply to fluoride ligands. Alkoxides and thiolates also destabilize active carbene conformations, while mesylate ligands lead to a balanced energetic relation of active and inactive carbene orientations. Cationic ruthenium carbene species with aqua or ammine ligands are limited by unfavored ligand dissociation to 14 valence-electron intermediates. A guideline for the design of novel ligand systems for ruthenium carbene complexes as metathesis catalysts is proposed. [source]
Bis(N,N,-dimethylimidazol-2-ylidene)mercury chlorotriiodomercury dimethyl sulfoxide solvateACTA CRYSTALLOGRAPHICA SECTION C, Issue 1 2000
Alex M. Clark
The double mercury salt [Hg(C5H8N2)2][HgClI3]·C2H6OS was prepared and its structure characterized. The [Hg(C5H8N2)2]2+ cation lies about an inversion centre and the [HgClI3]2, anion lies on a mirror plane. Cations and anions are linked to form a one-dimensional polymer by weak Hg,Cl interactions [Hg,Cl 3.3744,(3),Å]. The mercury,carbene bond distance [2.076,(7),Å] is typical of a dicationic mercury,carbene species. [source]
Platinum- and Gold-Catalyzed Rearrangement Reactions of Propargyl Acetates: Total Syntheses of (,)-,-Cubebene, (,)-Cubebol, Sesquicarene and Related TerpenesCHEMISTRY - A EUROPEAN JOURNAL, Issue 11 2006
Alois Fürstner Prof.
Abstract Propargyl acetates, in the presence of catalytic amounts of late transition-metal salts such as PtCl2 or AuCl3, represent synthetic equivalents of ,-diazoketones. This notion is corroborated by a concise approach to various sesquiterpene natural products starting from readily available substrates. Specifically, (+)-carvomenthone (17) is converted into propargyl acetate (S)- 26 by a sequence involving Stille cross-coupling of its kinetic enol triflate 18, regioselective hydroboration/oxidation of the resulting 1,3-diene 19, and addition of an alkynyl cerium reagent to aldehyde 21 thus obtained. Since the latter step was found to be unselective, the configuration of the reacting propargyl acetate was unambiguously set by oxidation followed by diastereoselective transfer hydrogenation by using Noyori's catalyst 25. Compound (S)- 26, on treatment with PtCl2 in toluene, converted exclusively to the tricyclic enol acetate 27, which was saponified to give norcubebone 11 in excellent overall yield. The conversion of this compound into the sesquiterpene alcohol (,)-cubebol (6) was best achieved with MeCeCl2 as the nucleophile, whereas the formation of the parent hydrocarbon (,)-,-cubebene (4) was effected in excellent yield by recourse to iron-catalyzed cross coupling methodology developed in this laboratory. Since norketone 11 has previously been transformed into (,)-,-cubebene (5) as well as (,)-4-epicubebol 8, our approach constitutes formal total syntheses of these additional natural products as well. Along similar lines, the readily available propargyl acetates 1, 33 and 47 were shown to give access to 2-carene 44, sesquicarene 39, and episesquicarene 51 in excellent overall yields. In this series, however, the cycloisomerization reaction was best achieved with catalytic amounts of AuCl3 in 1,2-dichloroethane as the solvent. In addition to these preparative results, our data provide some insight into the mechanism of these remarkable skeletal rearrangement reactions. Transformations of this type are likely triggered by initial coordination of the alkyne unit of the substrate to the carbophilic transition-metal cation. Formal attack of the alkene moiety onto the resulting ,-complex engenders the formation of an electrophilic cyclopropyl carbene species which subsequently reacts with the adjacent acetate unit to give the final product. The alternative phasing of events, implying initial attack of the acetate (rather than the alkene moiety) onto the metal,alkyne complex, is inconsistent with the stereochemical data obtained during this total synthesis campaign. [source]
Photo-Cross-Linked Small-Molecule Microarrays as Chemical Genomic Tools for Dissecting Protein,Ligand InteractionsCHEMISTRY - AN ASIAN JOURNAL, Issue 6 2006
Naoki Kanoh Dr.
Abstract We have developed a unique photo-cross-linking approach for immobilizing a variety of small molecules in a functional-group-independent manner. Our approach depends on the reactivity of the carbene species generated from trifluoromethylaryldiazirine upon UV irradiation. It was demonstrated in model experiments that the photogenerated carbenes were able to react with every small molecule tested, and they produced multiple conjugates in most cases. It was also found in on-array immobilization experiments that various small molecules were immobilized, and the immobilized small molecules retained their ability to interact with their binding proteins. With this approach, photo-cross-linked microarrays of about 2000 natural products and drugs were constructed. This photo-cross-linked microarray format was found to be useful not merely for ligand screening but also to study the structure,activity relationship, that is, the relationship between the structural motif (or pharmacophore) found in small molecules and its binding affinity toward a protein, by taking advantage of the nonselective nature of the photo-cross-linking process. [source]