The new C 7 Na minocyclitol kirkamide (1)w as isolated from leaf nodules of the plant Psychotria kirkii by using ag enome-driven 1 HNMR-guided fractionation approach.T he structure and absolute configuration were elucidated by HRMS,N MR, and single-crystal X-ray crystallography.A ne nantioselective total synthesis was developed, which delivered kirkamide (1)onagram scale in 11 steps and features aF errier carbocyclization and aP d-mediated hydroxymethylation. We propose that kirkamide is synthesized by Candidatus Burkholderia kirkii, the obligate leaf symbiont of Psychotria kirkii. Kirkamide (1)w as shown to be toxic to aquatic arthropods and insects,t hus suggesting that bacterial secondary metabolites playaprotective role in the Psychotria/ Burkholderia leaf nodule symbiosis.