Napredna pretraga

Pregled bibliografske jedinice broj: 587259

One catalyst for both enantiomers : uncovering the inversion of enantioselectivity in cinchona-mediated desymmetrization of glutaric meso-anhydrides


Ivšić, Trpimir; Novak, Jurica; Došlić, Nađa; Hameršak, Zdenko
One catalyst for both enantiomers : uncovering the inversion of enantioselectivity in cinchona-mediated desymmetrization of glutaric meso-anhydrides // Tetrahedron, 68 (2012), 39; 8311-8317 doi:10.1016/j.tet.2012.07.035 (međunarodna recenzija, članak, znanstveni)


Naslov
One catalyst for both enantiomers : uncovering the inversion of enantioselectivity in cinchona-mediated desymmetrization of glutaric meso-anhydrides

Autori
Ivšić, Trpimir ; Novak, Jurica ; Došlić, Nađa ; Hameršak, Zdenko

Izvornik
Tetrahedron (0040-4020) 68 (2012), 39; 8311-8317

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

Ključne riječi
desymmetrization; enantioselectivity; density functional calculations; asymmetric synthesis; hydrogen bonding

Sažetak
A puzzling inversion of enantioselectivity dependent on catalyst loading was observed during the quinine mediated desymmetrization of glutaric meso-anhydrides. This study presents the improvement of the catalytic path by carboxylic acids additives up to synthetically useful levels. The novel protocol utilizing 0.1 eq of alkaloid and xanthene-9-carboxylic acid at room temperature (RT) was found comparable to the protocol requiring 1.1 eq of alkaloid at -30 °C. Thus, by altering the protocol the same catalyst produces the opposite enantiomer. This occurrence was rationalized by an extensive computational study of the interactions governing the molecular complexes formed by quinine, methanol, 3-methylglutaric anhydride and the acetic acid. It was found that in a quinine catalysed reaction the alcohol and the anhydride were directly hydrogen bonded to the catalyst. On the other hand, in the reaction with additive the acid intercalates between the alcohol and quinine. Due to this insertion the alcohol approaches the anhydride from the opposite face, in agreement with the observed inversion of enantioselectivity.

Izvorni jezik
Engleski

Znanstvena područja
Kemija



POVEZANOST RADA


Projekt / tema
098-0352851-2921 - Kontrola atomske i molekulske dinamike oblikovanim elektromagnetskim poljima (Nađa Došlić, )
098-0982933-2908 - Kiralni građevni blokovi za biološki aktivne molekule. Sinteza i reaktivnost (Zdenko Hameršak, )

Ustanove
Institut "Ruđer Bošković", Zagreb

Profili:

Avatar Url Zdenko Hameršak (autor)

Avatar Url Nađa Došlić (autor)

Avatar Url Trpimir Ivšić (autor)

Avatar Url Jurica Novak (autor)

Citiraj ovu publikaciju

Ivšić, Trpimir; Novak, Jurica; Došlić, Nađa; Hameršak, Zdenko
One catalyst for both enantiomers : uncovering the inversion of enantioselectivity in cinchona-mediated desymmetrization of glutaric meso-anhydrides // Tetrahedron, 68 (2012), 39; 8311-8317 doi:10.1016/j.tet.2012.07.035 (međunarodna recenzija, članak, znanstveni)
Ivšić, T., Novak, J., Došlić, N. & Hameršak, Z. (2012) One catalyst for both enantiomers : uncovering the inversion of enantioselectivity in cinchona-mediated desymmetrization of glutaric meso-anhydrides. Tetrahedron, 68 (39), 8311-8317 doi:10.1016/j.tet.2012.07.035.
@article{article, year = {2012}, pages = {8311-8317}, DOI = {10.1016/j.tet.2012.07.035}, keywords = {desymmetrization, enantioselectivity, density functional calculations, asymmetric synthesis, hydrogen bonding}, journal = {Tetrahedron}, doi = {10.1016/j.tet.2012.07.035}, volume = {68}, number = {39}, issn = {0040-4020}, title = {One catalyst for both enantiomers : uncovering the inversion of enantioselectivity in cinchona-mediated desymmetrization of glutaric meso-anhydrides}, keyword = {desymmetrization, enantioselectivity, density functional calculations, asymmetric synthesis, hydrogen bonding} }

Časopis indeksira:


  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • Science Citation Index Expanded (SCI-EXP)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus


Citati