Isolation and Total Synthesis of Kirkamide, an Aminocyclitol from an Obligate Leaf Nodule Symbiont1. Issue 27 (1st June 2015)

• Record Type: Journal Article
• Authors: Sieber, Simon; Carlier, Aurélien; Neuburger, Markus; Grabenweger, Giselher; Eberl, Leo; Gademann, Karl
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 27(2015)
• Page Start: 7968
• Page End: 7970
• Publication Date: 2015-06-01
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201502696
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The new C₇N aminocyclitol kirkamide (<bold>1</bold>) was isolated from leaf nodules of the plant <italic>Psychotria kirkii</italic> by using a genome‐driven ¹H NMR‐guided fractionation approach. The structure and absolute configuration were elucidated by HRMS, NMR, and single‐crystal X‐ray crystallography. An enantioselective total synthesis was developed, which delivered kirkamide (<bold>1</bold>) on a gram scale in 11 steps and features a Ferrier carbocyclization and a Pd‐mediated hydroxymethylation. We propose that kirkamide is synthesized by <italic>Candidatus</italic> Burkholderia kirkii, the obligate leaf symbiont of <italic>Psychotria kirkii</italic>. Kirkamide (<bold>1</bold>) was shown to be toxic to aquatic arthropods and insects, thus suggesting that bacterial secondary metabolites play a protective role in the <italic>Psychotria/Burkholderia</italic> leaf nodule symbiosis.</p> </abstract>