A Synthetic Study towards the Marmycins and Analogues

Cañeque, Tatiana; Gomes, Filipe; Thi, Trang; Blanchard, Florent; Retailleau, Pascal; Gallard, Jean‐François; Maestri, Giovanni; Malacrìa, Max; Rodriguez, Raphaël

doi:10.1055/s-0035-1562627

Cited by 8 publications

(5 citation statements)

References 18 publications

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“…This strong glycosidic bond confers to such compounds a significantly enhanced in vivo resistance toward basic, acidic, and enzymatic hydrolysis . A plethora of C-aryl glycosides are found in nature and serve as key substrates in various biological mechanisms or are used as antitumor, antibiotic, and type II antidiabetic agents (Figure ). As an example, pseudouridine is the first modified C-nucleoside discovered in RNAs of living organisms.…”

Section: Introductionmentioning

confidence: 99%

Diastereoselective Pd-Catalyzed Anomeric C(sp³)–H Activation: Synthesis of α-(Hetero)aryl C-Glycosides

et al. 2021

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Anomeric C-H bond activation is an unsolved long-standing synthetic challenge. Herein we report a diastereoselective Pd-catalyzed anomeric C(sp 3 )-H activation methodology that allows the synthesis of elusive C-(hetero)arylglycosides with an exclusive α-selectivity.a Reactions were performed an oven dried re-sealable tube using sugar 1a (0.1 mmol), ArX 2 (3 equiv), Pd(OAc)2 (0.01 mmol), Ag2CO3 (3 equiv) in tAmOH (1.0 mL) at 120 °C. b Yield of isolated product.

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Section: Introductionmentioning

confidence: 99%

Diastereoselective Pd-Catalyzed Anomeric C(sp³)–H Activation: Synthesis of α-(Hetero)aryl C-Glycosides

et al. 2021

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“…625 Additionally, intramolecular Friedel− Crafts cyclization of 2-deoxyglycoside 699 induced by aqueous HBF 4 provided C-glycoside 700, albeit in low yield (13%). 626,627 12. SYNTHESIS OF C-GLYCOSIDES THROUGH REARRANGEMENT OF SUGAR PRECURSORS Construction of anomeric CC bonds through structural rearrangements of prerearranged sugar substrates, for example, Claisen rearrangement, Ramberg−Backlund rearrangement, and Wittig rearrangement, is considered to be an attractive approach for the preparation of C-glycosides.…”

Section: C-glycosylation With Glycosyl Imidates and Phosphatesmentioning

confidence: 99%

“… Furthermore, BF 3 ·OEt 2 -promoted glycosylation of 2-deoxyglycoside 695 with naphthol was carried out to yield β- C -aryl glucoside 696 in 60% yield. − C -Glycosylation of methyl 2-deoxy-riboside 697 with 2-bromofuran under the optimized conditions, namely, BF 3 ·OEt 2 as the promoter in a very short time (5 min), produced a mixture of C -glycoside 698 in 63% yield (α/β = 1:2.5) . Additionally, intramolecular Friedel–Crafts cyclization of 2-deoxyglycoside 699 induced by aqueous HBF 4 provided C -glycoside 700 , albeit in low yield (13%). , …”

Section: C-glycosylation With 1-o-methyl Sugarsmentioning

confidence: 99%

Recent Advances in the Chemical Synthesis of C-Glycosides

2017

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Advances in the chemical synthesis of C-pyranosides/furanosides are summarized, covering the literature from 2000 to 2016. The majority of the methods take advantage of the construction of the glycosidic C-C bond. These C-glycosylation methods are categorized herein in terms of the glycosyl donor precursors, which are commonly used in O-glycoside synthesis and are easily accessible to nonspecialists. They include glycosyl halides, glycals, sugar acetates, sugar lactols, sugar lactones, 1,2-anhydro sugars, thioglycosides/sulfoxides/sulfones, selenoglycosides/telluroglycosides, methyl glycosides, and glycosyl imidates/phosphates. Mechanistically, C-glycosylation reactions can involve glycosyl electrophilic/cationic species, anionic species, radical species, or transition-metal complexes, which are discussed as subcategories under each type of sugar precursor. Moreover, intramolecular rearrangements, such as the Claisen rearrangement, Ramberg-Bäcklund rearrangement, and 1,2-Wittig rearrangement, which usually involve concerted pathways, constitute another category of C-glycosylations. An alternative to the C-glycosylations is the formation of pyranoside/furanoside rings after construction of the predetermined glycosidic C-C bonds, which might involve cyclization of acyclic precursors or D-A cycloadditions. Throughout, the stereoselectivity in the formation of the resultant C-glycosidic linkages is highlighted.

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“…Following a procedure for preparation of a similar compound, 4 in a 50 mL round bottom flask equipped with a stir bar, 1-hydroxy-2-methoxyanthraquinone (0.2469 g, 0.971 mmol) was dissolved in 10 mL of dichloromethane and the solution was cooled to -78°C. Triethylamine (0.6 mL, 4.30 mmol) was added and the reaction mixture was stirred for 5 minutes.…”

Section: Fluorescencementioning

confidence: 99%

Photoacid Generators Activated Through Sequential Two-Photon Excitation: 1-Sulfonatoxy-2-alkoxyanthraquinone Derivatives

Zeppuhar¹,

Wolf²,

Falvey

2021

Preprint

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Two sulfonate ester derivatives of anthraquinone, 1-tosyloxy-2-methoxy-9,10-anthraquinone (1a) and 1-trifluoromethylsulfonoxy-2-methoxy-9,10-anthraquinone (1b) were prepared and their ability to produce strong acids upon photoexcitation was examined. It is shown that these compounds generate acid with a yield that increases with light intensity when the applied photon dose is held constant. Additional experiments show that the rate of acid generation increases 4 fold when visible light (532 nm) laser pulses are combined with ultraviolet (355 nm) compared with ultraviolet alone. Continuous wave diode laser photolysis also effects acid generation with a rate that depends quadratically on the light intensity. Density functional theory calculations, laser flash photolysis, and chemical trapping experiments support a mechanism whereby an initially formed triplet state (T1) is excited to a higher triplet state which in turn undergoes homolysis of the RS(O2)–OAr bond. Secondary reactions of the initially formed sulfonyl radicals produce strong acids. It is demonstrated that high intensity photolysis of either 1a or 1b can initiate cationic polymerization of ethyl vinyl ether.

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A Synthetic Study towards the Marmycins and Analogues

Cited by 8 publications

References 18 publications

Diastereoselective Pd-Catalyzed Anomeric C(sp³)–H Activation: Synthesis of α-(Hetero)aryl C-Glycosides

Diastereoselective Pd-Catalyzed Anomeric C(sp³)–H Activation: Synthesis of α-(Hetero)aryl C-Glycosides

Recent Advances in the Chemical Synthesis of C-Glycosides

Photoacid Generators Activated Through Sequential Two-Photon Excitation: 1-Sulfonatoxy-2-alkoxyanthraquinone Derivatives

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A Synthetic Study towards the Marmycins and Analogues

Cited by 8 publications

References 18 publications

Diastereoselective Pd-Catalyzed Anomeric C(sp3)–H Activation: Synthesis of α-(Hetero)aryl C-Glycosides

Diastereoselective Pd-Catalyzed Anomeric C(sp3)–H Activation: Synthesis of α-(Hetero)aryl C-Glycosides

Recent Advances in the Chemical Synthesis of C-Glycosides

Photoacid Generators Activated Through Sequential Two-Photon Excitation: 1-Sulfonatoxy-2-alkoxyanthraquinone Derivatives

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Product

Resources

About

Diastereoselective Pd-Catalyzed Anomeric C(sp³)–H Activation: Synthesis of α-(Hetero)aryl C-Glycosides

Diastereoselective Pd-Catalyzed Anomeric C(sp³)–H Activation: Synthesis of α-(Hetero)aryl C-Glycosides