Synlett 2017; 28(14): 1758-1762
DOI: 10.1055/s-0036-1588560
cluster
© Georg Thieme Verlag Stuttgart · New York

Efforts Toward a Synthesis of Crotogoudin and Crotobarin

Duy N. Mai
Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, CA 92697-2025, USA   eMail: cdv@uci.edu
,
Dmitriy Uchenik
Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, CA 92697-2025, USA   eMail: cdv@uci.edu
,
Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, CA 92697-2025, USA   eMail: cdv@uci.edu
› Institutsangaben
We thank the UC Cancer Research Coordinating Committee for funding initial phases of this research with grant CRC-15-380750 and the NSF for continued funding (CHE-1564340)
Weitere Informationen

Publikationsverlauf

Received: 11. Juli 2017

Accepted after revision: 07. August 2017

Publikationsdatum:
16. August 2017 (online)


Zoom Image

These authors contributed equally

Published as part of the ISHC Conference Special Section

Abstract

Two synthesis designs for the diterpenoid crotogoudin are discussed, and efforts to achieve each are described. First, a Cope rearrangement/intramolecular Diels–Alder cascade reaction was investigated. Second, a bioinspired sequence of cationic bicyclization and A-ring oxidative fragmentation set-up for a lactonization induced by a phenolic oxidation, ultimately providing a tricyclic intermediate that required only installation of the bridging ring of the salient bicyclo[2.2.2]octane system. This last endeavor was fraught with difficulty, but did lead to the development of conditions for cyclization of related keto-alkenes via manganese(III)-based radical chemistry.

Supporting Information