Hydroxylated Daphniphyllum Alkaloids from Daphniphyllum himalense

Abstract

Thirteen new hydroxylated calyciphylline A-type Daphniphyllum alkaloids (1-13) were isolated from an ethanolic extract of Daphniphyllum himalense. These structures were characterized on the basis of spectroscopic data analysis, especially from their 2D NMR spectra. Oxidation at the C-3, C-9, C-11, and C-12 positions is reported for the first time for this class of compounds. Selective compounds showed low inhibitory rates against three kinase enzymes, PTP1B, aurora A, and IKK-β, at a concentration of 20 μg/mL.

Integrating yeast chemical genomics and mammalian cell pathway analysis

“…3305-2 G4 is a known alkaloid called drupacine [41] (Fig. 5c), isolated from Cephalotaxus fortunei, whose structure was identified by spectroscopic data analysis [42]. 3305-2 G4 mapped to "mRNA processing" (Fig.…”

Total Syntheses of Daphenylline, Daphnipaxianine A, and Himalenine D

“…This hypothesis builds a linkage between 1 and a series of Daphniphyllum alkaloids from the calyciphylline A subfamily sharing a 6‐6‐5‐7‐5‐5‐hexacyclic core,, which inspired us to exploit this relationship from a synthetic perspective. Daphnipaxianine A ( 5 , Figure ) and himalenine D ( 6 ) are two oxygenated calyciphylline A type alkaloids isolated by the groups of Hao and Yue, respectively; they have not been synthesized to our knowledge. Herein, we report the total syntheses of 1 , 5 , and 6 .…”

“…[14] Am inor modification of their proposal is illustrated in Figure 1. Upon activation by acid, 2 could undergo Wagner-Meerwein-type ring expansion to arrive at hydroxycarboxylic acid 3;the strain of the congested spiro ring system may provide adriving force.Dehydration of 3 would generate diene 4.F urther decarboxylation followed by aromatization may give 1.This hypothesis builds alinkage between 1 and as eries of Daphniphyllum alkaloids from the calyciphylline As ubfamily sharing a6 -6-5-7-5-5-hexacyclic core, [1b,c] which inspired us to exploit this relationship from as ynthetic perspective.D aphnipaxianine A [15] (5,F igure 2) and himalenine D [16] (6)are two oxygenated calyciphylline A type alkaloids isolated by the groups of Hao and Yue, respectively;t hey have not been synthesized to our knowledge.Herein, we report the total syntheses of 1, 5,a nd 6.…”

Modular Assembly of Spirocarbocyclic Scaffolds through Pd0‐Catalyzed Intermolecular Dearomatizing [2+2+1] Annulation of Bromonaphthols with Aryl Iodides and Alkynes

“…The potential utility of our method is illustrated by the one-step construction of the polycyclic skeletons of dalesconols Aa nd Bf rom alkyne-tethered aryl iodides and 1-bromo-2-naphthol.Spirocyclicframeworks are commonly occurring structural motifs in many bioactive compounds [1] and have been used as core building blocks for awide range of functional materials [2] and chiral ligands. The potential utility of our method is illustrated by the one-step construction of the polycyclic skeletons of dalesconols Aa nd Bf rom alkyne-tethered aryl iodides and 1-bromo-2-naphthol.…”

“…Spirocyclicframeworks are commonly occurring structural motifs in many bioactive compounds [1] and have been used as core building blocks for awide range of functional materials [2] and chiral ligands. [3] Transition-metal-catalyzed dearomatization of aromatic systems,w hich offers unusual strategic disconnections,h ave proven to be ap owerful tool for accessing av ariety of challenging but synthetically valuable spirocyclic molecules.…”