Routes to nine-membered enediynes: not such a walk in the park

Lear, Martin (2015) Routes to nine-membered enediynes: not such a walk in the park. In: 64th Gordon Research Conference (GRC) on Natural Products 2015, July 26-31, 2015, Proctor Academy, Andover, NH, USA.

Full content URL: https://www.grc.org/programs.aspx?id=11732

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Item Type:Conference or Workshop contribution (Keynote)
Item Status:Live Archive

Abstract

The kedarcidin and C1027 chromophores are formidable targets for total synthesis. In this talk, I will describe viable routes to these highly unstable natural products. Over 20-years during our study of these nine-membered enediyne chromophores, several new methods may now be highlighted: stereoselective epoxyalkyne formation, atropselective Pd/Cu-Sonogashira coupling, 2-deoxy-α-glycosylation, CeX3-mediated enediyne cyclisation, and SmI2-based reductive olefination.

Further application of these methods to the biomimetic study of the putative enediyne-precursors of the cyanosporasides, sporolides, and fijiolides will also be presented. In particular, I will present biomimetic evidence of a p-benzyne diradical species reacting in either a radical mode (hydrogen abstraction) or ionic mode (chloride attack) at the same sterically exposed site, leading to either monochlorinated cyanosporaside A or cyanosporaside B, respectively. The ionic monochlorination of the cycloaromatized p-benzyne of the C1027 enediyne core to generate the fijiolide aglycon framework will also be disclosed for the first time (unpublished work).

Additional Information:Gordon Research Conference The Wide-Ranging Influence of Natural Products Research on Medicine and the Physical Sciences Session:- Innovations in the Synthesis of Biologically Active Natural Products
Keywords:Natural enediynes, Total synthesis, Organic methods
Subjects:F Physical Sciences > F160 Organic Chemistry
Divisions:College of Science > School of Chemistry
ID Code:17185
Deposited On:22 Apr 2015 16:50

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