A Pericyclic Reaction Cascade in Leporin Biosynthesis.

Published in: Angewandte Chemie (International ed. in English) (2018)

All roads lead to Rome: The biosynthesis of the leporins in Aspergillus sp. involves an unprecedented pericyclic reaction cascade. The enzyme LepI directs the periselectivity of a [4+2] cycloaddition towards a hetero-Diels-Alder reaction outcome to give the leporin molecular scaffold. The Diels-Alder side product is morphed into the leporin core structure by a LepI-catalyzed retro-Claisen rearrangement, culminating in efficient kinetic side product recycling.

Keyphrases

cell wall
electron transfer
room temperature