4.3 Review

Recent advances in transition-metal-catalyzed glycosyl cross-coupling reactions

Related references

Note: Only part of the references are listed.
Review Chemistry, Multidisciplinary

Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis

Amy Y. Chan et al.

Summary: The merger of photoredox catalysis with transition metal catalysis, known as metallaphotoredox catalysis, has become an important part of synthetic methodology. It combines the bond formation capability of transition metal catalysis with the utility of photoinduced electron and energy transfer processes. Photocatalytic substrate activation allows the involvement of simple starting materials in metal-mediated bond-forming processes, while electron or energy transfer with organometallic intermediates provides a complementary activation mode to traditional catalytic platforms.

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o-Cyanobenzoate: A Recyclable and Reusable Stereo-directing Group for β-O-Glycosylation via Pd(0)-catalyzed Ferrier Rearrangement

Pradip Das et al.

Summary: The study reports an efficient and stereoselective synthesis of 2,3-dideoxy-beta-O-glycosides from C3-(o-cyanobenzoate) ester protected glycal donors via Ferrier rearrangement under Pd(0)-catalyzed Tsuji-Trost conditions. The stereo-chemical outcome of the reactions was independent of the nature of protecting groups or conformational flexibility of the glycal donors. Incorporation of the directing group on the benzoate ester altered the reactivity for Tsuji-Trost as well as Ferrier Rearrangement pathway.

CHEMISTRY-AN ASIAN JOURNAL (2022)

Article Chemistry, Multidisciplinary

Excited-State Palladium-Catalyzed Radical Migratory Mizoroki-Heck Reaction Enables C2-Alkenylation of Carbohydrates

Wang Yao et al.

Summary: This research reports a strategy using excited-state palladium catalysis for the 1,2-radical migratory Mizoroki-Heck reaction, enabling C2-alkenylation of carbohydrates with 1-bromosugars and alkenes. The reaction shows tolerance to various functional groups and complex molecular architectures and expands the reactivity profile of excited-state Pd catalysis.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

Review Chemistry, Organic

Recent advances in palladium-catalyzed C(sp3)/C(sp2)-H bond functionalizations: access to C-branched glycosides

Zanjila Azeem et al.

Summary: In recent decades, there has been increasing interest in the transformation of complex substrates through C-H activation and functionalization. Palladium-catalyzed directing and non-directing group-assisted C-H functionalization has emerged as a powerful approach to access C-branched glycosides, but the site-selective functionalization of carbohydrates remains a challenge due to the complexity and stability of C-H bonds.

ORGANIC & BIOMOLECULAR CHEMISTRY (2022)

Article Chemistry, Organic

Stereoselective O-Glycosylation of Glycals with Arylboronic Acids Using Air as the Oxygen Source

Qiuyuan Wang et al.

Summary: An open-air palladium-catalyzed O-glycosylation method using glycals and arylboronic acids has been developed, allowing for the synthesis of various O-glycosides in high yields. Mechanistic studies revealed the origin of the chemo-/stereoselectivity in the reaction.

ORGANIC LETTERS (2022)

Article Chemistry, Multidisciplinary

Visible-Light-Promoted Stereoselective C(sp3)-H Glycosylation for the Synthesis of C-Glycoamino Acids and C-Glycopeptides

Rupeng Qi et al.

Summary: Visible-light-promoted and Cu-catalyzed stereoselective C-glycosylation allows for mild reaction conditions compatible with various carbohydrate substrates, leading to the synthesis of a wide variety of C-glycoamino acids and C-glycopeptidomimetics with good yields and excellent stereoselectivities. Dual-functional photocatalyst formed in situ plays a key role in catalyzing the photoredox process and controlling the stereoselectivity of the glycosylation reaction.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

Article Chemistry, Organic

One-Pot Stereoselective Synthesis of 2,3-Diglycosylindoles and Tryptophan-C-glycosides via Palladium-Catalyzed C-H Glycosylation of Indole and Tryptophan

Ya-Nan Ding et al.

Summary: A novel palladium-catalyzed C-H glycosylation method was described for the one-pot stereoselective synthesis of 2,3-diglycosylindoles and tryptophan-C-glycosides. The method offers a convenient and efficient route to construct C-glycosides using air and base-free and ligand-free conditions, and it can be applied to various glycosyl chloride donors.

ORGANIC LETTERS (2022)

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Ruthenium-Catalyzed Stereo- and Site-Selective ortho- and meta-C-H Glycosylation and Mechanistic Studies

Xue-Ya Gou et al.

Summary: This paper describes a new ruthenium-catalyzed method for the ortho- and meta-C-Ar-H glycosylation, resulting in the synthesis of various C-aryl pyranosides and furanosides. The method shows broad substrate scope and compatibility with different N-heterocyclic directing groups. Mechanistic studies suggest different pathways for ortho- and meta-C-Ar-H glycosylation, and density functional theory calculations provide an explanation for the high stereoselectivity observed in the meta-C-Ar-H glycosylation.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Synthesis and Glycosidation of Anomeric Halides: Evolution from Early Studies to Modern Methods of the 21st Century

Yashapal Singh et al.

Summary: Advances in synthetic carbohydrate chemistry have improved access to common glycans, but challenges remain. Glycosyl halides play a crucial role in glycosylation.

CHEMICAL REVIEWS (2022)

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Ruthenium-Catalyzed Pyridine-Directed Aryl C-H Glycosylation with Glycosyl Chlorides

Shaokun Cai et al.

Summary: Metal-catalyzed C-H glycosylation reactions are important strategies for the synthesis of C-glycosides. This study developed a new ruthenium catalyst for the ortho C-H glycosylation of arenes with various glycosyl chloride donors using a monodentate pyridine directing group.

JOURNAL OF ORGANIC CHEMISTRY (2022)

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Visible-Light-Induced Copper-Catalyzed Asymmetric C(sp3)-C(sp3)-H Glycosylation: Access to C-Glycopeptides

Ya-Nan Ding et al.

Summary: In this study, a practical and highly efficient method for visible-light-induced copper-catalyzed N-aminoquinoline-directed asymmetric C(sp(3))-C(sp(3))-H glycosylation was reported. Additionally, C-glycopeptides were synthesized through the glycosylation of nondeoxysugars with amino acids. This research provides a new approach for the synthesis of C-glycopeptides and C-glycoamino acids.

ORGANIC LETTERS (2022)

Article Chemistry, Multidisciplinary

C2-ketonylation of carbohydrates via excited-state palladium-catalyzed 1,2-spin-center shift

Gaoyuan Zhao et al.

Summary: This study reports the first direct strategy to synthesize C2-ketonyl-2-deoxysugars, important carbohydrate mimetics, from 1-bromosugars and silyl enol ethers via an excited-state palladium-catalyzed 1,2-spin-center shift process. The reaction is step-economic, has a broad substrate scope, high functional group tolerance, and can be used in the late-stage functionalization of natural product- and drug-glycoconjugates.

CHEMICAL SCIENCE (2022)

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Emerging Organometallic Methods for the Synthesis of C-Branched (Hetero)aryl, Alkenyl, and Alkyl Glycosides: C-H Functionalization and Dual Photoredox Approaches

Juba Ghouilem et al.

Summary: Transition-metal-catalyzed C-H functionalization and photoredox nickel dual catalysis are innovative approaches for the synthesis of C-branched glycosides, providing efficient and mild methods for accessing a variety of complex C-branched glycosides of great interest.

CHEMISTRY-A EUROPEAN JOURNAL (2021)

Article Chemistry, Multidisciplinary

Diastereoselective Synthesis of Aryl C-Glycosides from Glycosyl Esters via C-O Bond Homolysis

Yongliang Wei et al.

Summary: C-aryl glycosyl compounds offer improved in vivo stability compared to O- and N-glycoside analogues, making them attractive candidates for drug development and chemical biology studies. A new cross-coupling method has been developed for the preparation of C-aryl and heteroaryl glycosides, including nucleosides and 2-deoxysugars, from easily accessible glycosyl esters and bromoarenes, demonstrating the potential of this method in medicinal chemistry.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

Article Chemistry, Multidisciplinary

Excited-State Palladium-Catalyzed 1,2-Spin-Center Shift Enables Selective C-2 Reduction, Deuteration, and Iodination of Carbohydrates

Gaoyuan Zhao et al.

Summary: The study presents the first excited-state palladium-catalyzed 1,2-spin-center shift reaction for site-selective functionalization of carbohydrates. The strategy offers mild reaction conditions with high levels of selectivity, tolerating a wide range of functional groups and complex molecular architectures, suggesting a general approach for the rapid generation of natural and unnatural carbohydrates.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Recent advances in glycosylation involving novel anomeric radical precursors

Anrong Chen et al.

Summary: Radical glycosylation has emerged as a powerful method for synthesizing carbohydrate mimetics, with novel glycosyl radical precursors being identified for the synthesis of various glycosides. This review highlights recent advances in radical glycosylation and provides insights for future research directions.

JOURNAL OF CARBOHYDRATE CHEMISTRY (2021)

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Diastereoselective Synthesis of Thioglycosides via Pd-Catalyzed Allylic Rearrangement

Jiagen Li et al.

Summary: Stereoselective thioglycosylation via palladium-catalyzed allylic rearrangement was successfully achieved in this study, yielding various substituents on alpha-isomer thioglycosides. Additionally, a comprehensive series of aryl and benzyl thioglycosides were obtained through a combination of thiosulfates with glycals derived from different carbohydrates.

ORGANIC LETTERS (2021)

Article Chemistry, Organic

β-Glycosyl Trifluoroborates as Precursors for Direct α-C-Glycosylation: Synthesis of 2-Deoxy-α-C-glycosides

Daiki Takeda et al.

Summary: C-Glycosides are metabolically stable mimics of natural O-glycosides, synthesized through stereoinvertive sp(3)-sp(2) cross-coupling reactions using a photoredox/nickel dual catalytic system. The hydrogenation of vinyl C-glycosides leads to C-linked 2'-deoxydisaccharide analogues.

ORGANIC LETTERS (2021)

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Stereodivergent synthesis of C-glycosamino acids via Pd/Cu dual catalysis

Xiaoxiao Yan et al.

Summary: This study presents a stereodivergent synthesis of C-glycosamino acids via Pd/Cu dual catalysis, overcoming challenges such as the tolerance towards functional group density and the match/mismatch problems between chiral substrates and chiral ligand-metal complexes. The method allows for efficient preparation of diverse C-glycosamino acid derivatives, serving as crucial precursors for discovering new drugs and materials. This synthesis will accelerate the study of structural features, mode of action, and potential biological applications of C-glycosamino acids in the near future.

SCIENCE CHINA-CHEMISTRY (2021)

Article Chemistry, Applied

Stereoselective Preparation of C-Aryl Glycosides via Visible-Light-Induced Nickel-Catalyzed Reductive Cross-Coupling of Glycosyl Chlorides and Aryl Bromides

Ze-Dong Mou et al.

Summary: A new nickel-catalyzed cross-coupling reaction has been developed for the highly stereoselective synthesis of C-aryl glycosides using bench-stable glycosyl chlorides. The reaction proceeds smoothly under visible-light irradiation.

ADVANCED SYNTHESIS & CATALYSIS (2021)

Review Chemistry, Multidisciplinary

Exploiting non-covalent interactions in selective carbohydrate synthesis

Charles C. J. Loh

Summary: Non-covalent interactions are essential in bond-forming events, particularly in the realm of synthetic carbohydrate chemistry. The exploitation of NCIs has led to advancements in catalyzed glycosylations, glycofunctionalizations, and stabilization of intermediates. Additionally, emerging opportunities in utilizing halogen bonding and unconventional NCIs have shown promise in various aspects of carbohydrate chemistry.

NATURE REVIEWS CHEMISTRY (2021)

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Convergent Palladium-Catalyzed Stereospecific Arginine Glycosylation Using Glycals

Jun Yang et al.

Summary: This method allows effective arginine glycosylation, catalyzed by a palladium complex, which can be achieved in one step at room temperature with high functional group tolerance, facilitating the preparation of glycopeptide analogues.

ORGANIC LETTERS (2021)

Article Chemistry, Physical

Catalyst-Controlled Regiodivergent Synthesis of 1-and 3-Thiosugars with High Stereoselectivity and Chemoselectivity

Yuexin Liu et al.

Summary: An effective regiodivergent synthesis of 1- and 3-thiosugars was achieved using palladium and cobalt catalysis, respectively. The difference in the interaction of thiol moieties with Pd and Co catalysis conditions led to the selective formation of beta-1-thiosugars and (3S)-3-thiosugars. Experimental and theoretical calculations supported the proposed mechanism and provided insights into the regioselectivity based on the bond lengths of key intermediates.

ACS CATALYSIS (2021)

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Diastereoselective Decarboxylative Alkynylation of Anomeric Carboxylic Acids Using Cu/Photoredox Dual Catalysis

Mingxiang Zhu et al.

Summary: This study presents a simple route for the synthesis of alkynyl C-nucleosides using low-cost and nontoxic copper catalysis, demonstrating the power of Cu/photoredox dual catalysis in accessing highly complex glycosides under mild conditions.

ACS CATALYSIS (2021)

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Stereoselective Synthesis of C-Vinyl Glycosides via Palladium-Catalyzed C-H Glycosylation of Alkenes

Qikai Sun et al.

Summary: A new strategy has been developed for the stereoselective synthesis of C-vinyl glycosides, using Pd-catalyzed directed C-H glycosylation. This method offers a broadly applicable approach to streamline the synthesis of complex C-vinyl glycosides with high efficiency and excellent regio- and stereoselectivity.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

Article Chemistry, Multidisciplinary

Synthesis of C-Mannosylated Glycopeptides Enabled by Ni-Catalyzed Photoreductive Cross-Coupling Reactions

Runyu Mao et al.

Summary: Researchers have developed a novel method using Ni-catalyzed cross-coupling conditions to achieve tryptophan C-mannosylation, successfully synthesizing and studying glycopeptides. Through this method, they not only successfully identified an antibody epitope, but also completed the synthesis of an insect hormone.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

Article Chemistry, Multidisciplinary

Nickel-Catalyzed Radical Migratory Coupling Enables C-2 Arylation of Carbohydrates

Gaoyuan Zhao et al.

Summary: Nickel catalysis offers exciting opportunities for addressing challenges in organic synthesis. A novel nickel-catalyzed radical migratory cross-coupling reaction was reported for the direct preparation of 2-aryl-2-deoxyglycosides from readily available 1-bromosugars and arylboronic acids. This reaction shows a broad substrate scope, high tolerance to functional groups, and efficient synthesis of valuable carbohydrate mimics and building blocks.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Eric M. Miller et al.

Summary: This study presents stereoselective C-arylation and etherification reactions of anomeric trifluoroborates derived from BMIDA esters, exhibiting high anomeric selectivities for 2-deoxysugars and showing a broad substrate scope, including disaccharides and trifluoroborates with free hydroxyl groups. This new class of carbohydrate reagents adds to the palette of anomeric nucleophile reagents suitable for efficient installation of C-C bonds.

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Yan-Hua Liu et al.

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Advances in Pd-catalyzed C-C bond formation in carbohydrates and their applications in the synthesis of natural products and medicinally relevant molecules

Nazar Hussain et al.

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