Generation of the new quirogane skeleton by a vinylogous retro-Michael type rearrangement of longipinene derivatives

Román, Luisa U.; Morales, Nicole; Hernández, José Falcón; Cerda-Garcı́a-Rojas, Carlos M.; Zepeda, L. Gerardo; Flores-Sandoval, César A.; Joseph‐Nathan, Pedro

doi:10.1016/s0040-4020(01)00718-9

Cited by 19 publications

(11 citation statements)

References 11 publications

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“…Their phytochemical studies started almost four decades ago with the structure elucidation of rastevione ( 1 ), which is easily available from the hexanes extracts of the roots of S. serrata . Since then, the longipinane skeleton has inspired the study of molecular rearrangements, − since it possesses a central strained four-membered ring simultaneously holding a six- and a seven-membered ring in 1,3 dispositions. The chemical exploration of these substances has led to the discovery of new carbocyclic scaffolds obtained through a series of molecular rearrangements promoted by the strategic location of functional groups on the tricyclic skeleton, which act as leaving groups when the four-membered ring strain is released.…”

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Novel Sesquiterpene Skeletons by Multiple Wagner–Meerwein Rearrangements of a Longipinane-1,9-diol Derivative

et al. 2019

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The tricyclic sesquiterpene (1R,3R,4S,5S,7S,8S,9S,10R,11R)-7,8-diangeloyloxylongipinan-1,9-diol, or rasteviol (7), underwent multiple Wagner–Meerwein molecular rearrangements and several hydride shifts when treated with Et2O–BF3 to generate the six new compounds (1R,3R,4S,5R,7S,8S,9S,10R,11S)-7,8-diangeloyloxy-1,9-epoxyjiquilpane (8), (1R,3R,4S,5R,7R,8S,9S,11S)-8-angeloyloxy-1,7-epoxyzamor-10(14)-ene (11), (2S,3R,4R,5R,6R,7R,8S,9S,10S)-7,8-diangeloyloxy-6,9-epoxyjanitziane (14), (4R,5R,7S,8S,9S,10S,11S)-7,8-diangeloyloxy-9-hydroxyjiquilp-3(15)-ene (16), (2S,3S,5R,7S,8R,10S,11R)-7,8-diangeloyloxyiratzian-9-one (18), and (2S,3S,5R,10S,11R)-8-angeloyloxyiratzi-7-en-9-one (22), of which 8, 11, 14, and 18 possess new hydrocarbon skeletons. Their structures were determined by 1D and 2D NMR in combination with single-crystal X-ray diffraction analyses of derivatives 10, 15, 20, and 21, which allowed confirmation of their absolute configurations by means of the Flack and Hooft parameters. In addition, some reaction mechanism information was gained from deuterium labeling experiments.

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Novel Sesquiterpene Skeletons by Multiple Wagner–Meerwein Rearrangements of a Longipinane-1,9-diol Derivative

et al. 2019

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“…The positions C-7, C-8, C-9, and C-13 are usually oxidazed with acyloxy and/or hydroxyl groups and a keto function is present at C-1 which is α,β-unsaturated in most compounds [ 1 ]. Longipinenes are highly oxygenated tricyclic structures with a spatial configuration susceptible to different types of rearrangements [ 17 ]. The absolute configuration of most longipinanes isolated from Stevia spp.…”

Section: Phytochemistrymentioning

confidence: 99%

Stevia Genus: Phytochemistry and Biological Activities Update

et al. 2021

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The Stevia genus (Asteraceae) comprises around 230 species, distributed from the southern United States to the South American Andean region. Stevia rebaudiana, a Paraguayan herb that produces an intensely sweet diterpene glycoside called stevioside, is the most relevant member of this genus. Apart from S. rebaudiana, many other species belonging to the Stevia genus are considered medicinal and have been popularly used to treat different ailments. The members from this genus produce sesquiterpene lactones, diterpenes, longipinanes, and flavonoids as the main types of phytochemicals. Many pharmacological activities have been described for Stevia extracts and isolated compounds, antioxidant, antiparasitic, antiviral, anti-inflammatory, and antiproliferative activities being the most frequently mentioned. This review aims to present an update of the Stevia genus covering ethnobotanical aspects and traditional uses, phytochemistry, and biological activities of the extracts and isolated compounds.

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“…Thus, irradiation of the (+)-enone 339 yields the (+)-adduct 340, by a 1,5-cyclization mode, and the (−)-adduct 341, by the 1,6-mode, in 45% and 15% yield, respectively 218 . The unsaturated δ-lactone 342 undergoes intramolecular photochemical (2 + 2)-cycloaddition to afford the product 343 219 and a further strained cyclobutane is reported by irradiation of 344 that yields adduct 345 220 . Examples of intramolecular cycloadditions have been reported that can be carried out enantioselectively in the presence of the complexing agent 346.…”

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confidence: 99%

Photochemistry of Cyclobutanes: Synthesis and Reactivity

Horspool

2009

Patai's Chemistry of Functional Groups

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Introduction Cycloaddition Reactions Involving Alkenes Cycloaddition Reactions Involving Dienes and Trienes Cycloadditions of Enones and Related Compounds Photochemistry of Ketones Cage Compounds Cyclobutane Ring Opening Reactions

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Generation of the new quirogane skeleton by a vinylogous retro-Michael type rearrangement of longipinene derivatives

Cited by 19 publications

References 11 publications

Novel Sesquiterpene Skeletons by Multiple Wagner–Meerwein Rearrangements of a Longipinane-1,9-diol Derivative

Novel Sesquiterpene Skeletons by Multiple Wagner–Meerwein Rearrangements of a Longipinane-1,9-diol Derivative

Stevia Genus: Phytochemistry and Biological Activities Update

Photochemistry of Cyclobutanes: Synthesis and Reactivity

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