title: Lipophilic oligopeptides for chemo- and enantioselective acyl transfer reactions onto alcohols.
abstract: Inspired by the extraordinary selectivities of acylases, we envisioned the use of lipophilic oligopeptidic organocatalysts for the acylative kinetic resolution/desymmetrization of rac- and meso-cycloalkane-1,2-diols. Here we describe in a full account the discovery and development process from the theoretical concept to the final catalyst, including scope and limitations. Competition experiments with various alcohols and electrophiles show the full potential of the employed oligopeptides. Additionally, we utilized NMR and IR-spectroscopic methods as well as computations to shed light on the factors responsible for the selectivity. The catalyst system can be readily modified to a multicatalyst by adding other catalytically active amino acids to the peptide backbone, enabling the stereoselective one-pot synthesis of complex molecules from simple starting materials.
authors.affiliation: Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, 35392 Giessen, Germany.
authors.forename: Christian E
authors.initials: CE
authors.lastname: Müller
authors.forename: Daniela
authors.initials: D
authors.lastname: Zell
authors.forename: Radim
authors.initials: R
authors.lastname: Hrdina
authors.forename: Raffael C
authors.initials: RC
authors.lastname: Wende
authors.forename: Lukas
authors.initials: L
authors.lastname: Wanka
authors.forename: Sören M M
authors.initials: SM
authors.lastname: Schuler
authors.forename: Peter R
authors.initials: PR
authors.lastname: Schreiner
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009842:Oligopeptides / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000438:Alcohols; D009842:Oligopeptides