Negishi Cross‐Coupling Provides Alkylated Tryptophans and Tryptophan Regioisomers

Mild transition‐metal catalysed cross‐couplings enable direct functionalisation of biocatalytically halogenated tryptophans with alkyl iodides, representing a new alternative for late‐stage derivatisations of halogenated aromatic amino acids. Moreover, this strategy enables preparation of (homo)tryptophan regioisomers in a simple two‐step synthesis using a Pd‐catalysed Negishi cross coupling. This method provides access to non‐canonical constitutional surrogates of tryptophan, ready for use in peptide synthesis.