"Backdoor induction" of chirality: asymmetric hydrogenation with rhodium(I) complexes of triphenylphosphane-substituted beta-turn mimetics

Kokan, Zoran; Glasovac, Zoran; Majerić Elenkov, Maja; Gredičak, Matija; Jerić, Ivanka; Kirin, Srećko I.

doi:10.1021/om5005385

Pregled bibliografske jedinice broj: 706979

"Backdoor induction" of chirality: asymmetric hydrogenation with rhodium(I) complexes of triphenylphosphane-substituted beta-turn mimetics

Kokan, Zoran; Glasovac, Zoran; Majerić Elenkov, Maja; Gredičak, Matija; Jerić, Ivanka; Kirin, Srećko I.

"Backdoor induction" of chirality: asymmetric hydrogenation with rhodium(I) complexes of triphenylphosphane-substituted beta-turn mimetics // Organometallics, 33 (2014), 15; 4005-4015 doi:10.1021/om5005385 (međunarodna recenzija, članak, znanstveni)

CROSBI ID: 706979 Za ispravke kontaktirajte CROSBI podršku putem web obrasca

Naslov
"Backdoor induction" of chirality: asymmetric hydrogenation with rhodium(I) complexes of triphenylphosphane-substituted beta-turn mimetics

Autori
Kokan, Zoran ; Glasovac, Zoran ; Majerić Elenkov, Maja ; Gredičak, Matija ; Jerić, Ivanka ; Kirin, Srećko I.

Izvornik
Organometallics (0276-7333) 33 (2014), 15; 4005-4015

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
amino acids; artificial metalloenzymes; asymmetric catalysis; DFT calculations; metallated bioconjugates; supramolecular chemistry

Sažetak
Bioconjugate bidentate ligands 2−10 were 8 obtained by tethering triphenylphosphanecarboxylic acid to amino acid substituted spacers with different flexibility, ranging from a rigid enediyne-based β-turn inducer to flexible linear aliphatic chains with up to eight carbon atoms. The 21 synthesized ligands revealed up to 81% ee selectivity in rhodium-catalyzed asymmetric hydrogenation of α, β-unsaturated amino acids. The key feature of the catalysts is the prochiral coordination sphere of the catalytic metal while the chirality is transmitted by “backdoor induction” from distant hydrogen-bonded amino acids. DFT calculations were applied to study the structure and relative stability of the precatalytic organometallic Rh(I) complexes, with particular emphasis on hydrogen-bonded secondary structures.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA

Projekti:
098-0982904-2946 - Višenuklearni metalni sustavi: sinteza i svojstva (Perić, Berislav, MZOS ) ( CroRIS)
COST Action CM1105
UKF 36/08
098-0982933-2908 - Kiralni građevni blokovi za biološki aktivne molekule. Sinteza i reaktivnost (Hameršak, Zdenko, MZOS ) ( CroRIS)
098-0982933-2936 - Kemijske preobrazbe prirodnih spojeva (Varga-Defterdarović, Lidija, MZOS ) ( CroRIS)
HRZZ-02.04/23 - Metalirani biokonjugati za primjene u istraživanju materijala i u biomedicini (MBABMS) (Kirin, Srećko, HRZZ ) ( CroRIS)