A Versatile Diquinane from Fulvene as a Building Block in Natural Product Synthesis. 1. A Facile Synthesis of the Iridoids Loganin and Sarracenin

Tai, Huo-Mu; Chang, Meng‐Yang; Lee, † and An-Yang; Chang, Nein-Chen

doi:10.1021/jo9817624

Cited by 18 publications

(5 citation statements)

References 29 publications

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“…Chang and co-workers have adopted a similar protocol toward the total synthesis of iridoid natural products loganin 80 and sarracenin 81 . The intermediate for both of the natural products was obtained from the versatile diquinane 78 , which was afforded from the [2+2] cycloaddition reaction of 6-acetoxyfulvene 75 with the in situ generated methylchloroketene (Scheme ).…”

Section: Cycloaddition Chemistry Of Pentafulvenesmentioning

confidence: 99%

“…Chang and co-workers have adopted a similar protocol toward the total synthesis of iridoid natural products loganin 80 and sarracenin 81. 94 The intermediate for both of the natural products was obtained from the versatile diquinane 78, which was afforded from the [2+2] cycloaddition reaction of 6- As mentioned earlier, pentafulvene displays different reactivity patterns with different cycloaddition partners. In the early 1970s, Houk et al revealed that fulvene acted as a 4π component with the tetraene system of tropone, affording a double [6+4]-type adduct.…”

Section: Pentafulvene As 2π Componentsmentioning

confidence: 99%

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Recent Advances in the Chemistry of Pentafulvenes

et al. 2017

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Pentafulvenes are a unique class of compounds that originally attracted attention due to their propensity to display nonbenzenoid aromaticity. Subsequently, they were recognized as valuable synthons for the construction of a wide range of compounds by virtue of their ability to display multiple cycloaddition profiles. Naturally, this area of organic chemistry has experienced rapid growth over the last five decades, fueled by elegant work showcasing the unique reactivity of pentafulvenes in a plethora of cycloaddition reactions. In this Review, we have attempted to provide a systematic account of the methods for the generation of pentafulvenes, their rich and varied cycloaddition chemistry, organometallic reactions, and theoretical studies that support their versatility. Further, we have highlighted their applications in the synthesis of a variety of complex structural frameworks. It is our conviction that this Review will be useful to a wide range of chemists, and will spur further research in this promising area.

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Section: Cycloaddition Chemistry Of Pentafulvenesmentioning

confidence: 99%

Section: Pentafulvene As 2π Componentsmentioning

confidence: 99%

Recent Advances in the Chemistry of Pentafulvenes

et al. 2017

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“…Besides, Au‐Yeung et al demonstrated that allylsilanes can be applied to a total synthesis of loganin by using the reaction of allylsilanes with electrophiles, and the results show that this method has a higher yield than the previous method (Au‐Yeung & Fleming, 1977) (Figure 4). In addition, Tai et al also successfully synthesized loganin using versatile diquinane as the key intermediate (Tai, Chang, Lee, & Chang, 1999).…”

Section: Synthesis Of Loganinmentioning

confidence: 99%

Phytochemistry, synthesis, analytical methods, pharmacological activity, and pharmacokinetics of loganin: A comprehensive review

Zhang

et al. 2022

Phytotherapy Research

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Iridoid glycosides (IGs) are found in many medicinal and edible plants, such as Gardenia jasminoides, Cistanche tubulosa, Eucommia ulmoides, Rehmanniae Radix, Lonicera japonica, and Cornus officinalis. Loganin, an IG, is one of the main active ingredient of Cornus officinalis Sieb. et Zucc., which approved as a medicinal and edible plant in China. Loganin has been widely concerned due to its extensive pharmacological effects, including anti‐diabetic, antiinflammatory, neuroprotective, and anti‐tumor activities, etc. Studies have shown that these underlying mechanisms include anti‐oxidation, antiinflammation and anti‐apoptosis by regulating a variety of signaling pathways, such as STAT3/NF‐κB, JAK/STAT3, TLR4/NF‐κB, PI3K/Akt, MCP‐1/CCR2, and RAGE/Nox4/p65 NF‐κB signaling pathways. In order to better understand the research status of loganin and promote its application in human health, this paper systematically summarized the phytochemistry, analysis methods, synthesis, pharmacological properties and related mechanisms, and pharmacokinetics based on the research in the past decades.

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“…Ther esulting molecules are planar with C 2v point groups and 1 A 1 electronic ground states in the case of 1-3, whereas nonafulvene (4)adopts atwisted geometry (C 2 )with a 1 Ae lectronic ground state owing to inefficient conjugation of the exocyclic carbon-carbon double bond with the nine-membered ring. [5,6] Theu nique reactivity associated with the cross-conjugated p-electronic structure has led to the broad use of fulvenes in the synthesis of natural products,s uch as loganin and sarracenin, [7,8] and in transition-metal complexes, such as {(h 5 -C 5 Me 5 )Ti(h 6 -C 5 H 4 = C(pC 7 H 7 ) 2 )} 2 (m 2 ,h 1 ,h 1 -N 2 ). [9,10] Fulvenes also serve as fundamental molecular building blocks in fluorescent aromatic hydrocarbons,including 9-(cycloheptatrienylidene)fluorene, [11] 9-(methylidenecyclopropabenzene)fluorene,a nd 5-(methylidenecyclopropabenzene)dibenzocycloheptatriene.…”

Section: Introductionmentioning

confidence: 99%

Directed Gas‐Phase Synthesis of Triafulvene under Single‐Collision Conditions

Thomas

Zhao

et al. 2019

Angew Chem Int Ed

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The triafulvene molecule (c‐C4H4)—the simplest representative of the fulvene family—has been synthesized for the first time in the gas phase through the reaction of the methylidyne radical (CH) with methylacetylene (CH3CCH) and allene (H2CCCH2) under single‐collision conditions. The experimental and computational data suggest triafulvene is formed by the barrierless cycloaddition of the methylidyne radical to the π‐electron density of either C3H4 isomer followed by unimolecular decomposition through elimination of atomic hydrogen from the CH3 or CH2 groups of the reactants. The dipole moment of triafulvene of 1.90 D suggests that this molecule could represent a critical tracer of microwave‐inactive allene in cold molecular clouds, thus defining constraints on the largely elusive hydrocarbon chemistry in low‐temperature interstellar environments, such as that of the Taurus Molecular Cloud 1 (TMC‐1).

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A Versatile Diquinane from Fulvene as a Building Block in Natural Product Synthesis. 1. A Facile Synthesis of the Iridoids Loganin and Sarracenin

Cited by 18 publications

References 29 publications

Recent Advances in the Chemistry of Pentafulvenes

Recent Advances in the Chemistry of Pentafulvenes

Phytochemistry, synthesis, analytical methods, pharmacological activity, and pharmacokinetics of loganin: A comprehensive review

Directed Gas‐Phase Synthesis of Triafulvene under Single‐Collision Conditions

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