Transition metal-mediated condensation

Transition-metal mediated condensation of esters and aldehydes is known. The reaction of a thioester and an aryl aldehyde with TiCLi—NBU3, for example, gave a p-hydroxy thioester with good syn selectivity. Selenoamides [RCH2C(=Se)NRy react with EDA and then an aldehyde to give p-hydroxy selenoamides. ... 

Pyrrolo[3,2-df pyridazines are a class of interesting and useful A -heterocycles [40—42]. However, synthetic methods for such heterocyclic compounds have been very much limited such as condensation of pyrrole-2,3-diones with hydrazine. There are no reports on one-pot multi-component synthesis of pyrrolo[3,2-(f py-ridazines [43]. Moreover, synthetic methods for pyrrole-2,3-diones are also very limited [43]. On the other hand, transition-metal-mediated reactions of azides are of great importance and versatility in organic synthesis, because azides could be readily transformed into a wide variety of valuable A -containing natural products and medicinal agents [44-50]. 

Intramolecular condensation of co-hydroxycarboxylic acids is a standard method to prepare lactones. Acid catalysts or more elaborate mediators are usually required as well as continuous removal of water. Transition-metal-catalyzed cyclocarbonylation of unsaturated alcohols is a fascinating alternative, which proceeds under neutral conditions [26]. Intramolecular hydroesterification of... 

Applications of electrospray mass spectrometry (ESMS) to the study of reactions mediated by transition-metal complexes are reviewed. ESMS has become increasingly popular as an analytical tool in inorganic and organometallic chemistry, in particular with regard to the identification of short-lived intermediates of catalytic cycles. Going one step further, the coupling of electrospray ionization to ion-molecule techniques in the gas phase yields detailed information about single reaction steps of catalytic cycles. This method allows the study of transient intermediates that have previously not been within reach of condensed-phase techniques on both a qualitative and quantitative level. 

Because they have low vapor pressures, transition metals cannot be loaded by direct adsorption, but their adsorption can be mediated by transient organo-metallic complexes formed between zerovalent metal atoms and solvent molecules. This is the basis of the solvated metal atom dispersion (SMAD) method developed by Klabunde and Tanaka [72]. Metal vapors condensed in Hquid hydrocarbons at low temperatures form weak complexes that are easily decomposed even below room temperature. Microporous supports impregnated with solutions of metal complexes at low temperatures are warmed up to decompose the complex and liberate zerovalent metal atoms which nucleate into clusters. Preparation of Ni- and Co-clusters in HY and HZSM-5 was reported [72]. In the same way, Nazar et al. [64] condensed iron and cobalt vapors in a slurry of dehydrated NaY zeolite in toluene at -120 °C, then the mixture was rotated at-78°C. The bis-toluene complex thus formed and adsorbed in the zeoUte was decomposed by warming to room temperature yielding clusters small enough to fit into supercages. 

The problematic nature of the melting transition can be illustrated by comparison with other well-known first-order phase transitions, for instance the normal metal-(low T ) superconductor transition. The normal metal-superconductor and melting transitions have similar symptomatic definitions, the former being a loss of resistance to current flow, and the latter being a loss of resistance to shear. However, superconductivity can also be neatly described as a phonon-mediated (Cooper) pairing of electrons and condensation of Cooper pairs into a coherent ground state wave function. This mechanistic description of the normal metal-super-conductor transition has required considerable theoretical effort for its development, but nevertheless boils down to a simple statement, indicat-... 

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