Lipophilic Oligopeptides for Chemo- and Enantioselective Acyl Transfer Reactions onto Alcohols

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 t...

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Bibliographic Details
Published in:Journal of organic chemistry 2013-09, Vol.78 (17), p.8465-8484
Main Authors: Müller, Christian E, Zell, Daniela, Hrdina, Radim, Wende, Raffael C, Wanka, Lukas, Schuler, Sören M. M, Schreiner, Peter R
Format: Article
Language:English
Subjects:
Alcohols - chemical synthesis
Alcohols - chemistry
Magnetic Resonance Spectroscopy
Models, Molecular
Molecular Structure
Oligopeptides - chemistry
Stereoisomerism
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Summary: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo401195c