Non-ribosomal peptide cyclases that catalyse head-to-tail macrocyclization are repurposed here to enable regioselective macrocyclization of branched peptides with multiple nucleophiles, affording lariat-shaped peptides with various sequences and ring sizes. Coupled with subsequent site-selective acylation chemistry, this chemoenzymatic approach facilitates modular access to structurally diverse lariat lipopeptides.
- Masakazu Kobayashi
- Kenichi Matsuda
- Toshiyuki Wakimoto
