Synfacts 2019; 15(11): 1217
DOI: 10.1055/s-0039-1691049
Synthesis of Natural Products and Potential Drugs
© Georg Thieme Verlag Stuttgart · New York

Total Synthesis of Illisimonin A

Erick M. Carreira
Felix Pultar
Burns AS, Rychnovsky SD. * University of California, Irvine, USA
Total Synthesis and Structure Revision of (–)-Illisimonin A, a Neuroprotective Sesquiterpenoid from the Fruits of Illicium simonsii .

J. Am. Chem. Soc. 2019;
141: 13295-13300
Further Information

Publication History

Publication Date:
18 October 2019 (online)



Burns and Rychnovsky report on the first total synthesis of illisimonin A, a sesquiterpenoid isolated from the fruits of Illicium simonsii. The combination of an intramolecular Diels–Alder reaction with a semi-pinacol rearrangement enables the rapid access of the target molecule’s core structure. Using a resolution strategy, the authors are also able to produce enantioenriched (–)-ilisimonin A.



Enone B is generated from simple starting materials. A 1,3-dioxa-2-silacyclohexenetemplated Diels–Alder reaction yields the congested intermediate D. Functional group interconversion leading to epoxide F pave the route for the crucial semi-pinacol rearrangement. Ultimately, functional group interconversions and a final directed C–H oxidation give rise to the natural product.