Daphmacropomines A–E: Five Daphniphyllum Alkaloids from Daphniphyllum macropodum Miq.

Five new Daphniphyllum alkaloids, daphmacropomines A–E (1–5), were isolated from Daphniphyllum macropodum Miq. and structurally characterized. Compound 1 is an unprecedented Daphniphyllum alkaloid that features a unique 6/9/7/5/5 ring with a rare N-nitroso group. Compound 2 is the second Daphniphyllum alkaloid featuring a highly rearranged 6/6/6/7/5/6-fused skeleton. Compounds 3 and 4 are new yuzurimine-type alkaloids, and their structures were determined by extensive techniques including HRESIMS, NMR, ECD, and single-crystal X-ray. A plausible biosynthetic pathway for 1–4 is proposed. Furthermore, compounds 3 and 4 can induce lysosomal biogenesis and promote autophagic flux.