Total Synthesis of Complex & Unstable Nine-membered Enediynes

Lear, Martin (2017) Total Synthesis of Complex & Unstable Nine-membered Enediynes. In: Lecture Tour, January 2017, Osaka Prefecture University, Osaka Institute of Technology, Sophia University, 8-22 January 2016, Japan.

Abstract _Lear_2017.pdf
Abstract _Lear_2017.pdf - Abstract

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


The kedarcidin and C1027 chromophores are formidable targets for total synthesis. Herein, we describe viable routes to these highly unstable natural products. Over the 20 or so years of studying these nine-membered enediyne chromophores, several new methods may now be highlighted from our efforts: 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 are also summarized. 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 presented.

Keywords:Total synthesis, organic chemistry
Subjects:F Physical Sciences > F160 Organic Chemistry
Divisions:College of Science > School of Chemistry
ID Code:32222
Deposited On:20 Oct 2018 20:58

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