Glycopeptide Assembly via Selective Manganese(I)-Catalyzed C–H Alkenylations in Organic Media and in Water

Abstract

Glycopeptides are key structural motifs of powerful pharmaceuticals and of relevance for the molecular understanding in the life sciences. Despite major advances, the synthesis of glycopeptides largely relies on prefunctionalized substrates and lengthy synthesis sequences. In sharp contrast, the assembly of diverse glycopeptides has now been accomplished under exceedingly mild reaction conditions by manganese-catalyzed C–H alkenylations with ample scope. The C–H activation strategy was characterized by distinctive elements of regio-, site-, and chemo-selectivities with structurally complex substrates at room temperature by a benign manganese catalyst. The distinct power of our approach was mirrored by the assembly of hybrid glycopeptides featuring various fluorogenic labels with large Stokes shifts. The robust nature of our manganese(I) catalyst was reflected by its full tolerance for water as a reaction medium in micellar catalysis.