title: Site-Selective Acylations with Tailor-Made Catalysts.
abstract: The acylation of alcohols catalyzed by N,N-dimethylamino pyridine (DMAP) is, despite its widespread use, sometimes confronted with substrate-specific problems: For example, target compounds with multiple hydroxy groups may show insufficient selectivity for one hydroxyl, and the resulting product mixtures are hardly separable. Here we describe a concept that aims at tailor-made catalysts for the site-specific acylation. To this end, we introduce a catalyst library where each entry is constructed by connecting a variable and readily tuned peptide scaffold with a catalytically active unit based on DMAP. For selected examples, we demonstrate how library screening leads to the identification of optimized catalysts, and the substrates of interest can be converted with a markedly enhanced site-selectivity compared with only DMAP. Furthermore, substrate-optimized catalysts of this type can be used to selectively convert "their" substrate in the presence of structurally similar compounds, an important requisite for reactions with mixtures of substances.
authors.affiliation: Organic Chemistry, Bergische Universität Wuppertal, Gaußstr. 20, 42119, Wuppertal, Germany.
authors.forename: Florian
authors.initials: F
authors.lastname: Huber
authors.affiliation: Organic Chemistry, Bergische Universität Wuppertal, Gaußstr. 20, 42119, Wuppertal, Germany. sfkirsch@uni-wuppertal.de.
authors.forename: Stefan F
authors.identifier: http://orcid.org/0000-0003-2628-8703
authors.initials: SF
authors.lastname: Kirsch
keywords: acylations; catalysis; libraries; peptides; regioselectivity