Progress on total synthesis and their divergent transformations of aryltetrahydrofuran-type lignans

Yao, Sichen; Xiao, Jian; Guo, Nan; Peng, Yu

doi:10.1016/j.tetlet.2022.154309

Cited by 6 publications

(3 citation statements)

References 48 publications

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“…It was worth mentioning that the products from this methodology were generally α-branched ketones, which could be stereoselectively manipulated to branched homoallyl alcohols 53 . Moreover, such α-branched β,γ-unsaturated ketones and the corresponding homoallyl alcohols were highly practical building blocks in organic synthesis [54][55] .…”

Section: Figure 3 | Elucidation Of the Selectivities Of The 12-migrat...mentioning

confidence: 99%

Generation and Wagner-Meerwein Rearrangement of α-Carbonyl Cations from Brønsted Acid-Catalyzed Alkyne Oxidations with Pyridine N-Oxides

Wang

Zhou

Zuo

et al. 2023

Preprint

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α-Carbonyl cations are the umpolung forms of the synthetically fundamental α-carbonyl carbanions. They are highly reactive yet rarely studied and utilized species and their precursors were rather limited. Herein, we report the generation of α-carbonyl cations from HNTf2-catalyzed alkyne oxidations with pyridine N-oxides and the interception of them via Wagner-Meerwein rearrangement. Broad spectrum of alkynes including aryl alkyne, ynamide, and alkynyl sulfide could be utilized and the migrating priorities of different groups in the Wagner-Meerwein rearrangement step was elucidated. DFT calculations further supported the generation of α-carbonyl cations via the N-O bond cleavage. Another key feature of this methodology was the fragmentation of synthetically inert tert-butyl groups into readily transformable olefin functionalities. The synthetic potential was highlighted by the scale-up reaction and the downstream diversifications including the formal synthesis of nicotlactone B and galbacin.

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Section: Figure 3 | Elucidation Of the Selectivities Of The 12-migrat...mentioning

confidence: 99%

Generation and Wagner-Meerwein Rearrangement of α-Carbonyl Cations from Brønsted Acid-Catalyzed Alkyne Oxidations with Pyridine N-Oxides

Wang

Zhou

Zuo

et al. 2023

Preprint

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“…On the other hand, the tetrahydrofuran moiety is broadly present in biologically active natural products of both terrestrial and marine organisms, and as such, it has raised the attention of communities of synthetic and medicinal chemists . Also, thiolane cycle-containing natural products, and their synthetic analogs have found therapeutic applications, been studied as antibiotics, antiviral, and anticancer agents or have been used in traditional Ayurvedic medicine to treat the metabolic syndrome …”

Section: Introductionmentioning

confidence: 99%

1,2-Silyl Shift-Induced Heterocyclization of Propargyl Silanes: Synthesis of Five-Membered Heterocycles Containing a Functionalized Olefin Side Chain

Kroņkalne,

Beļaunieks,

Ubaidullajevs

et al. 2023

J. Org. Chem.

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Propargyl silanes with a terminal alkyne moiety undergo a 1,2-silyl shift when activated with electrophiles such as H+, Br+, I+, and PhSe+. A method was developed to trap 1,3-transposed electrophilic centers with various internal O-, N-, and S-nucleophiles in a 5-exo manner. This synthetic procedure provided five-membered heterocycles containing a trisubstituted olefin side chain. The scope of the method includes access to tetrahydrofuran, γ-butyrolactone, 2-isooxazoline, pyrrolidine, and thiolane derivatives in yields ranging from 25 to 85% (23 examples in total). Reactions with TsNBr2 ensured complete (E)-selectivity of the newly formed olefins. Further functionalization of the obtained 1-trialkylsilyl-2-bromovinyl side chain was demonstrated by double-bond geometry-preserving electrophilic substitution and cross-coupling reactions that provided heterocycles with a trisubstituted vinyl moiety.

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“…While She’s group has pursued the synthesis of isoabietenin A ( 1 ), to the best of our knowledge, there have been no reported total syntheses or a study of the structure–activity relationships (SARs) for these novel [6-5-6-6] tetracyclic abietane diterpenoids. As part of our continued interest in the total syntheses of bioactive natural products with a tetrahydrofuran ring, we chose epoxyhinokiol ( 2 ) as our initial target and studied its SARs.…”

mentioning

confidence: 99%

Photocatalytic Tandem Radical Cyclization Enables Expeditious Total Synthesis of Epoxyhinokiol Analogues for Anticancer Activity Evaluation

Xiao,

Wu,

Liang

et al. 2024

Org. Lett.

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A photocatalytic radical cascade with an unusual endo-trig cyclization was developed, which enables the efficient assembly of divergent tricyclic diterpenoid frameworks. The first total synthesis of abietane 10-epi-epoxyhinoliol was thus achieved in six steps by a subsequent reductive coupling of i-PrBr under photoredox/nickel dual catalysis. Inhibitory tests of chiral 10-epiepoxyhinoliol and its analogues in 4T1 cancer cells demonstrated the critical role of the C12 hydroxyl group, leading to a discovery of the simplified analogue with better activity.

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Progress on total synthesis and their divergent transformations of aryltetrahydrofuran-type lignans

Cited by 6 publications

References 48 publications

Generation and Wagner-Meerwein Rearrangement of α-Carbonyl Cations from Brønsted Acid-Catalyzed Alkyne Oxidations with Pyridine N-Oxides

Generation and Wagner-Meerwein Rearrangement of α-Carbonyl Cations from Brønsted Acid-Catalyzed Alkyne Oxidations with Pyridine N-Oxides

1,2-Silyl Shift-Induced Heterocyclization of Propargyl Silanes: Synthesis of Five-Membered Heterocycles Containing a Functionalized Olefin Side Chain

Photocatalytic Tandem Radical Cyclization Enables Expeditious Total Synthesis of Epoxyhinokiol Analogues for Anticancer Activity Evaluation

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