Protected dipeptides can be converted into cyclic ketoaminals, which can be subjected to palladium-catalyzed regioselective C−H functionalization. The best results are obtained using the 2-(methylthio)aniline (MTA) directing group, which is superior to the commonly used 8-aminoquinoline (AQ) group. No epimerization of stereogenic centers is observed. Subsequent cleavage of the directing and protecting groups allows the incorporation of a modified dipeptide into larger peptide chains.

Brominated and iodinated allylic substrates can be subjected to palladium‐catalyzed allylic alkylation of amino acid and peptide ester enolates. The incorporation of a vinylic halide functionality into the allylic substrate allows a direct modification of the allylated peptide via cross coupling chemistry. Therefore, the direct introduction of a vinylhalide side chain into a peptide is an interesting alternative to the stannylallylation/halogenation approach. However, the haloallylation is not as trivial as normal allylic alkylations, because the incorporation of a second, competitive electrophilic center into the allyl moiety requires careful optimization of the reaction conditions.

Myxoprincomide, a secondary metabolite of the myxobacterium Myxococcus xanthus DK 1622, is synthesised for the first time. The central, unusual α-ketoamide is generated at the end of the syn-thesis to...

Tetradeuterated (S)-lysine can easily be obtained from protected (S)-serine in a few steps including a Cu-mediated cross coupling and subsequent platinum-catalysed deuteration.

Matteson homologations and a Pd-catalysed C–H functionalisation are key steps in the synthesis of highly selective HDAC1 inhibitor WF-3161.