Kalshinoids A–F, Anti-inflammatory Sesquiterpenes from Kalimeris shimadae

Abstract

In a study of the potential anti-inflammatory constituents from Kalimeris shimadae, six new sesquiterpenes, kalshinoids A–F (1–6), together with 21 known compounds (7–27), were isolated. The structures and absolute configurations of the new compounds were discerned from extensive spectroscopic analysis, and the absolute configurations of kalshinoids A, B, E, and F were established by ECD calculations. Furthermore, the identified compounds were tested for anti-inflammatory activity as assessed by inhibition of tumor necrosis factor-alpha (TNF-α) in THP-1 cells. Three sesquiterpenes [kalshinoid F, 4(15)-eudesmen-1β,7,11-triol, and 4α,10α,11-trihydroxy-1βH,5βH-guai-7­(8)-ene] reduced levels of TNF-α in lipopolysaccharide-stimulated THP-1 cells in a concentration-dependent manner and were more potent than dexamethasone. These natural sesquiterpenes merit further investigation as possible anti-inflammatory agents.

Four New Sesquiterpenoids from Zanthoxylum nitidum

“…The 13 C‐NMR ( Table 1) and HSQC spectroscopic information of 3 could be assigned for 15 carbon signals, including two olefinic carbons ( δ C 139.6 and 124.3), five methylene groups ( δ C 67.4, 42.9, 27.6, 23.5 and 23.0), four methine groups ( δ C 51.2, 48.1, 40.9, and 27.2), a quaternary carbon ( δ C 72.9), and three methyl groups ( δ C 21.9, 20.5 and 15.5). Comprehensive analysis of NMR data demonstrated that 3 had a same planar structure as 10β,15‐hydroxy‐α‐cadinol, [13] and then this conclusion was verified via the detailed 2D NMR correlation ( Figure 2). The difference being the presence of the NOE correlation between H‐1 and H‐14, and the difference of spatial configuration of 3 was demonstrated based on a NOESY test.…”

“…The presence of NOE correlations between H-1/H-6, H-1/H-10/H-13, and H-12/H-14 (Figure 3 quaternary carbon (δ C 72.9), and three methyl groups (δ C 21.9, 20.5 and 15.5). Comprehensive analysis of NMR data demonstrated that 3 had a same planar structure as 10β,15-hydroxy-α-cadinol, [13] and then this conclusion was verified via the detailed 2D NMR correlation (Figure 2). The difference being the presence of the NOE correlation between H-1 and H-14, and the difference of spatial configuration of 3 was demonstrated based on a NOESY test.…”

“…The 1 H-NMR information of 1 displayed the presence of three methyl protons [δ H 1.25 (3H, s), 1.14 (3H, s) and 1.01 (3H, s)]. Subsequently, its 13 C-NMR spectrum (Table 1) combined with the HSQC spectrum, showed 15 carbon signals, comprising two sp 2 carbons (δ C 143.6 and 130.7), five methylene groups (δ C 65.4, 39.3, 33.2, 29.5 and 22.9), three methine groups (δ C 50.0, 33.2, 26.5), three methyl group (δ C 28.8, 24.4 and 16.4) as well as two quaternary carbons (δ C 81.7 and 19.7). The detailed 1D NMR data displayed that 1 might be a sesquiterpenoid derivative, and the chemical structure of 1 was highly like that of isospathulenol, [11] the main difference is that the disappearance of a methyl instead of the presence of a methylene.…”

“…a 1 H (600 MHz) and13 C (150 MHz) NMR data were obtained in CD 3 OD. b 1 H (400 MHz) and13 C (100 MHz) NMR data were obtained in CD 3 OD.…”

Cytotoxic Sesquiterpenoids from Atractylodes chinensis (DC.) Koidz.

“…The NOESY correlations ( Figure 3) of H‐1 β/ Me‐14 and H‐1 α /H‐5 indicated Me‐14 and H‐5 to be β ‐ and α ‐oriented, respectively. Comparing CD data with known compound, it was verified that the absolute configuration of 2 was 5 S ,10 S [11] …”