A Pericyclic Reaction Cascade in Leporin Biosynthesis.

Angew Chem Int Ed Engl

Biosystems Chemistry, Department of Chemistry and Center for Integrated Protein Science Munich (CiPSM), Technical University of Munich (TUM), Lichtenbergstraße 4, 85748, Garching, Germany.

Published: March 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.

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http://dx.doi.org/10.1002/anie.201800629DOI Listing

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