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Karbeny N-heterocykliczne : synteza i zastosowanie

Malinowska M., Hryniewicka A.

Wiadomości Chemiczne

2015

[Z] 69, 3-4

227--253

N-Heterocyclic carbenes (NHCs) are powerful tools in organic chemistry, with numerous applications in academic and industrial laboratories. They are usually defined as singlet carbenes, in which the divalent carbonic centre is connected directly to at least one nitrogen atom in the heterocycle [1]. They have played an important role in organic chemistry ever since the first evidence of their existence. The isolation of stable, free 1,3‑diadamantylimidazol-2-ylidene (IAd, Fig. 1) by Arduengo et al. in 1991 was a milestone in the chemistry of carbenes [2]. From the beginnings as academic curiosities, N‑heterocyclic carbenes today are very useful compounds in a variety of organic transformations (Fig. 13). NHCs are neutral σ-donors, which form very strong bonds with the majority of transition metals (stronger than phosphines). These compounds are easy-to-make ligands with great potential in homogeneous catalysis (mainly ruthenium and palladium complexes) for large number of reactions, including the coupling reactions (Heck, Negishi, Stille, Suzuki or Sonogashira reactions) and olefin metathesis [3]. Moreover, they are very useful as organocatalysts used in the benzoin condensation, the Stetter reaction and ring-opening polymerization (ROP) or transesterification [4]. In this review, we aim to give an overview of the properties and applications of NHCs, which we expect will be a useful introduction for chemists interested in studying and applying these important compounds. The first part of this review is devoted to the main synthetic routes to NHCs, their properties and reactivity. In the second part we describe the metal complexes with NHCs as homogeneous catalysts and their applications in various types of reactions. At the end of this part of the paper the use of NHCs as organocatalysts is presented.

Synteza i zastosowanie nowych katalizatorów metatezy olefin

Hryniewicka A.

Wiadomości Chemiczne

2014

[Z] 68, 11-12

961--980

Olefin metathesis has emerged as a powerful tool for the formation of carboncarbon double bonds. The success of this methodology has spurred the intense investigation of new catalysts showing a better application profile. The syntheses and the application profiles of the seven new ruthenium metathesis catalysts have been described. Five of them were modified in benzylidene part with 6-hydroxychromane- and 2H-3,4-chromenemethylidene moiety. In chromanol – α-tocopherol model compound, some specific stereoelectronic effects have been observed. Introduction of this ligand to the catalyst may provide new advantageous properties. The other new catalysts contained modified N-heterocyclic carbene ligand (NHC), in which N,N’-mesityl substituents of NHC system were linked with diethylene glycol chain as a “clamping ring”. This ring would contribute to a steric shield of the NHC and ruthenium coordination center. Probably it may inforce a proper orientation of substituents in metallacyclobutane (all-cis), leading to Z-olefin formation. The obtained catalysts were investigated in model reactions: ring closing metathesis, cross metathesis and enyne metathesis. The experiments proved they efficiency. In many reactions the catalysts showed activity comparable or superior to that of commercially available Grubbs and Hoveyda 2nd generation complexes. Stereochemistry Z/E of the cross-metathesis products obtained using new and known complexes were similar as well. The catalysts were applied in the synthesis of a new type of α-tocopherol glycoconjugates. An efficient method of the synthesis Hoveyda 2nd type complexes starting from ruthenium trichloride was developed. It is possible to circumvent using special laboratory equipment and expensive reagents. Hoveyda type complexes can be achieved with very good yield in gram scale. Keywords: