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Synthesis of (-)-Ilimaquinone via a Radical Decarboxylation and Quinone Addition Reaction

Taotao Ling, Erwan Poupon, Erik J. Rueden, and Emmanuel A. Theodorakis*

*Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, California 92093-0358, Email: etheodorucsd.edu

T. Ling, E. Poupon, E. J. Rueden, E. A. Theadorakis, Org. Lett., 2002, 4, 819-822.

DOI: 10.1021/ol025501z


Abstract

The stereoselective synthesis of (-)-ilimaquinone is based on a radical decarboxylation and quinone addition methodology that produces a quinone derivative from reaction of thiohydroxamic acid derivative with benzoquinone. Final functionalization of this intermediate to ilimaquinone is achieved by exploring the electronic effects of the residual thiopyridyl group.

Radical decarboxylation and quinone addition:



Details

An efficient synthesis of (-) ilimaquinone is based on a novel radical decarboxylation and quinone addition methodology that was used to construct the carbocyclic framework of the natural product. Taking advantage of both the electronic effects and the leaving ability of the residual thiopyridyl group, conditions for sequential regioselective oxygenations of the quinone ring were developed. The strategy extends the scope, applicability, and versatility of the above methodology and opens the way for the construction of differentially substituted derivatives of the natural product.


Key Words

Barton Decarboxylation


ID: J54-Y2002-890