Naslov
The application of "backdoor induction" in bioinspired asymmetric catalysis

Autori
Kirin, Srećko I.

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
Book of Abstracts / Bonačić-Koutecky, Vlasta - Split, 2012, Suppl.-suppl.

Skup
NATO Advanced Research Workshop: Multidisciplinary Endeavour in Nanobiology, Nanoscience and Environment

Mjesto i datum
Split, Hrvatska, 16.04.2012. - 20.04.2012

Vrsta sudjelovanja
Pozvano predavanje

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
homogeneous catalysis; Rh(I) complexes; amino acids; hydrogen bonding

Sažetak
In recent years, the catalysis of chemical reactions has an enormous impact in industry ; the production of most important chemicals involves a catalytic step. Catalysis is particularly important in the synthesis of chiral compounds ; a small amount of a chiral catalyst can produce large quantities of chiral products from prochiral substrates. Asymmetric (enantioselective) catalysis draws its inspiration from nature. Since the lock-and-key specificity of natural systems often results in a limited scope, organic synthesis of natural and non-natural compounds offers a more flexible approach and is complementary to biological synthesis. Chiral metal complexes are used as homogeneous asymmetric catalysts very frequently. The general importance of the incorporation of the chiral information as close as possible to the coordination sphere of the metal, where the actual catalysis takes place, is widely accepted. Within our project, we challenge this fundamental principle and use a catalytically active metal centre that is only prochiral. The chiral information is transmitted by "backdoor induction" via hydrogen bonding between distant pedant amino acids. An artificial C2-symmetrical peptide turn structure is formed that controls the chirality of the catalysts coordination sphere. Preliminary results were obtained on Rh(I) catalyzed asymmetric hydrogenation of model substrates, with selectivities up to 82% ee.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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