Highly Oxygenated Guaianolides and Eudesman-12-oic Acids from Balsamorhiza sagittata and Balsamorhiza macrophylla

Mohamed, Abou El‐Hamd H.; Ahmed, Ahmed A.; Wollenweber, Eckhard; Bohm, Bruce A.; Asakawa, Yoshinori

doi:10.1248/cpb.54.152

Cited by 8 publications

(17 citation statements)

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“…The structures 389 or 390 were proposed. The exudates of the aerial parts of Balsamorhiza sagittata and Balsamorhiza macrophilla 354 contain the new guaiane derivative 391. A study of a methanolic extract from the fruits of Torilis japonica 355 afforded the cytotoxic sesquiterpenes torilin 392, 1ahydroxy-torilin 393 and the new metabolite 1b-hydroxy-torilin 394.…”

Section: Guaiane Pseudoguaiane Xanthane and Patchoulanementioning

confidence: 99%

Natural sesquiterpenoids

Fraga

2010

Nat. Prod. Rep.

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Section: Guaiane Pseudoguaiane Xanthane and Patchoulanementioning

confidence: 99%

Natural sesquiterpenoids

Fraga

2010

Nat. Prod. Rep.

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“…This ever-growing class of important secondary metabolites possesses a wide range of biological properties, which include plant growth inhibition, insect antifeedant, antibacterial, antifungal, and antitumor activities. Representative eudesmanes include antibacterial agents (+)-carissone ( 1 ) and (+)-3-oxocostusic acid ( 2 ), as well as P/Q-type calcium channel blocker (−)-α-eudesmol ( 3 ) (Figure ). These examples typify common structural motifs within this class of sesquiterpenoids, including the C(10) all-carbon quaternary stereocenter and stereogenic C(7) substituent.…”

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confidence: 99%

Catalytic Enantioselective Approach to the Eudesmane Sesquiterpenoids: Total Synthesis of (+)-Carissone

2008

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A catalytic enantioselective approach to the eudesmane sesquiterpenoids is reported. The strategic use of a palladium-catalyzed enantioselective alkylation of vinylogous ester substrates forged the C (10) all-carbon quaternary center. This key transformation enabled a diastereoselective olefin hydrogenation to create the syn stereochemistry at C(7). The devised synthetic strategy allowed for the preparation of the antibacterial agent (+)-carissone and a formal synthesis of the P/Q-type calcium channel blocker (-)-α-eudesmol.The flowering plants of the family Asteraceae (Compositae) have many historical uses, including rubber, medicines, edible oils, vegetables, and pesticides. 1 Among these flora are a large number of species that are abundant in structurally diverse sesquiterpenoids, particularly ones that contain the eudesmane skeleton (Figure 1). Over 1000 eudesmanes have been identified from these sources, with their structures diverging based on oxygenation and oxidation patterns within the carbon framework.This ever-growing 2 class of important secondary metabolites possesses a wide range of biological properties, including plant growth inhibition, insect antifeedant, antibacterial, antifungal, and antitumor activities. Representative eudesmanes include antibacterial agents (+)-carissone (1) 3 and (+)-3-oxocostusic acid (2), 4 as well as P/Q-type calcium channel blocker (−)-α-eudesmol (3) 5 (Figure 1). These examples typify common structural motifs within this class of sesquiterpenoids, including the C(10) all-carbon quaternary stereocenter and stoltz@caltech.edu. In devising a strategy for the total synthesis of the eudesmanes, we simplified our target to enone 5, which has been utilized in the preparation of structures such as 4, 6d and itself embodies many features present in various family members (cf. 5 and 1, 2) ( Figure 2). We envisioned that the stereochemistry of the C(7) substituent could arise by means of the diastereoselective hydrogenation of a substituted cyclohexene (i.e., 6), the stereochemical outcome of which would be controlled by the C(10) quaternary stereocenter. This cyclohexene could be obtainable from a ring-closing methathesis of triolefin 7, which would be derived from an appropriately substituted α-quaternary ketone (i.e., 8). Thus, the key control element in the design of this synthetic strategy is the C(10) quaternary stereocenter, 10 and we therefore sought to develop an efficient and selective means for the preparation of this moiety. NIH Public AccessThe enantioselective alkylation of ketone enolates is an area of intense investigation in our laboratory. 11 This method has resulted in the preparation of wide range of carbonyl compounds with adjacent quaternary stereocenters with high levels of selectivity and excellent yields, some of which have proved valuable in synthetic endeavors. 12 The application of α-quaternary ketones such as 8 for the devised strategy would require a carbonyl transposition (i.e., 8 → 7), and we therefore chose to exploit the unique propert...

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“…Compound 1 was purified in a white amorphous powder. The 1 H NMR spectrum of 1 observed characteristic signals of 5 olefinic protons at δH 6.29 Measured at a) CDCl3, b) 125 MHz, c) 500 MHz, #) Reported by Mohamed et al, [13] $) Reported by Quijano et al, [14] NR) Not reported. Signals were assigned based on HSQC and HMBC experiments.…”

Section: Resultsmentioning

confidence: 99%

“…9β-Acetoxy-3-epi-nobilium (1): H NMR (500 MHz, CD3OD) δH in ppm: 7.76 (1H, dd, J = 2.0 and 8.0 Hz, H-6), 7.53 (1H, dt, J = 2.0 and 8.0 Hz, H-4), 7.40 (1H, dd, J = 2.0 and 8.0 Hz, H-3), 7.13 (1H, dt, J = 2.0 and 8.0 Hz, H-5), 3.90 (3H,s, 7-OCH3); sugar moiety: 4.90 (1H, d, J = 7.5, Glc H-1), 3.91 (1H, dd, J = 2.0 and 12.0, Glc Ha-6), 3.74 (1H, dd, J = 5.5 and 12.0, Glc Hb-6), 3.55 (1H, t, J = 9.0, Glc H-4), 3.54 (1H, t, J = 9.0, Glc H-3), 3.48 (1H, m, Glc H-5), 3.44 (1H, dd, J = 7.5 and 9.0, Glc H-2); 13 C NMR (125 MHz, CD3OD) δC in ppm: 168.6 (C-7), 158.7 (C-2), 135.1 (C-4), 132.0 (C-6), 123.7 (C-5), 122.4 (C-1), 119.0 (C-3), 52.8 (7-OCH3); sugar moiety: 104.1 (Glc C-1), 78.5 (Glc C-5), 77.5 (Glc C-3), 75.1 (Glc C-2), 71.3 (Glc C-4), 62.6 (Glc C-6); HR-ESI-MS: found m/z 349.0686 [M+ 35 Cl] -, calcd. for [C14H18O8 35 Cl] -: 349.0696, Δ = -2.8 ppm, found m/z 351.0666 [M+ 37 Cl] -, calcd.…”

Section: Extraction and Isolationmentioning

confidence: 99%

“…Ficuside G (6): 1 H NMR (500 MHz, CD3OD) δH in ppm: 7.73 (1H, dd, J = 2.0 and 8.0 Hz, H-6), 7.51 (1H, dt, J = 2.0 and 8.0 Hz, H-4), 7.28 (1H, dd, J = 2.0 and 8.0 Hz, H-3), 7.08 (1H, dt, J = 2.0 and 8.0 Hz, H-5), 3.90 (3H, s, 7-OCH3); sugar moiety: 5.17 (1H, d, J = 7.5 Hz, Glc H-1), 3.68 (1H, dd, J = 7.5 and 9.0 Hz, Glc H-2), 3.87 (1H, dd, J = 2.0 and 12.0 Hz, Glc Ha-6), 3.72 (1H, dd, J = 5.0 and 12.0 Hz, Glc Hb-6), 5.26 (1H, d, J = 1.5 Hz, Rham H-1), 3.96 (1H, dd, J = 1.5 and 3.0 Hz, Rham H-2), 1.04 (3H, d, J = 7.0 Hz, Rham H-6); 13 C NMR (125 MHz CD3OD) δC in ppm: 168.7 (C-7), 157.7 (C-2), 123.2 (C-1), 117.4 (C-3), 134.5 (C-4), 122.9 (C-5), 132.0 (C-6), 52.7 (7-OCH3); sugar moiety: 100.9 (Glc C-1), 80.6 (Glc C-2), 78.…”

Section: Extraction and Isolationmentioning

confidence: 99%

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Investigation on chemical constituents from Sigesbeckia orientalis L.

Trang,

Trang

2023

Vietnam Journal of Chemistry

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Two germacranolide sesquiterpenes, 9β‐acetoxy‐3‐epi‐nobilium (1), zoapatanolide B (2) and four benzoate ester derivatives, benzyl 2‐O‐β‐D‐glucopyranosyl‐6‐methoxybenzoate (3), benzyl 2‐O‐β‐D‐glucopyranosyl‐6‐hydroxybenzoate (4), methyl 2‐O‐β‐D‐glucopyranosylbenzoate (5), ficuside G (6) were isolated from aerial part of Sigesbeckia orientalis. Structural elucidation of the isolated compounds was done using a combination of HR‐ESI‐MS, one‐dimensional and two‐dimensional NMR spectral methods, and comparison their spectral data with the previous literature. This is the first description of the structural identification of these compounds from S. orientalis.

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Highly Oxygenated Guaianolides and Eudesman-12-oic Acids from Balsamorhiza sagittata and Balsamorhiza macrophylla

Cited by 8 publications

References 8 publications

Natural sesquiterpenoids

Natural sesquiterpenoids

Catalytic Enantioselective Approach to the Eudesmane Sesquiterpenoids: Total Synthesis of (+)-Carissone

Investigation on chemical constituents from Sigesbeckia orientalis L.

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