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Uncovering Key Structural Features of an Enantioselective Peptide-Catalyzed Acylation Utilizing Advanced NMR Techniques
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SYSNO ASEP 0470637 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Uncovering Key Structural Features of an Enantioselective Peptide-Catalyzed Acylation Utilizing Advanced NMR Techniques Tvůrce(i) Procházková, Eliška (UOCHB-X) RID, ORCID
Kolmer, A. (DE)
Ilgen, J. (DE)
Schwab, M. (DE)
Kaltschnee, L. (DE)
Fredersdorf, M. (DE)
Schmidts, V. (DE)
Wende, R. C. (DE)
Schreiner, P. R. (DE)
Thiele, C. M. (DE)Zdroj.dok. Angewandte Chemie - International Edition. - : Wiley - ISSN 1433-7851
Roč. 55, č. 51 (2016), s. 15754-15759Poč.str. 6 s. Jazyk dok. eng - angličtina Země vyd. DE - Německo Klíč. slova conformational analysis ; enantioselective acylations ; NMR spectroscopy ; pure shift NMR ; RDCs Vědní obor RIV CC - Organická chemie Institucionální podpora UOCHB-X - RVO:61388963 UT WOS 000390599400005 EID SCOPUS 85003480062 DOI https://doi.org/10.1002/anie.201608559 Anotace We report on a detailed NMR spectroscopic study of the catalyst-substrate interaction of a highly enantioselective oligopeptide catalyst that is used for the kinetic resolution of trans-cycloalkane-1,2-diols via monoacylation. The extraordinary selectivity has been rationalized by molecular dynamics as well as density functional theory (DFT) computations. Herein we describe the conformational analysis of the organocatalyst studied by a combination of nuclear Overhauser effect (NOE) and residual dipolar coupling (RDC)-based methods that resulted in an ensemble of four final conformers. To corroborate the proposed mechanism, we also investigated the catalyst in mixtures with both trans-cyclohexane-1,2-diol enantiomers separately, using advanced NMR methods such as T-1 relaxation time and diffusion-ordered spectroscopy (DOSY) measurements to probe molecular aggregation. We determined intramolecular distance changes within the catalyst after diol addition from quantitative NOE data. Finally, we developed a pure shift EASY ROESY experiment using PSYCHE homodecoupling to directly observe intermolecular NOE contacts between the trans-1,2-diol and the cyclohexyl moiety of the catalyst hidden by spectral overlap in conventional spectra. All experimental NMR data support the results proposed by earlier computations including the proposed key role of dispersion interaction. Pracoviště Ústav organické chemie a biochemie Kontakt asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418 Rok sběru 2017
Počet záznamů: 1