Visible-Light-Induced Copper-Catalyzed Asymmetric C(sp<sup>3</sup>)–C(sp<sup>3</sup>)–H Glycosylation: Access to C-Glycopeptides

Ding, Yanan; Li, Ning; Huang, Yan‐Chong; An, Yang; Liang, Yong‐Min

doi:10.1021/acs.orglett.2c01501

Cited by 21 publications

(17 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Notably, the deprotection or protecting-group conversion of C -glycoamino acids proceeded smoothly using simple procedures, which preserved the diastereomeric ratio (Scheme ). After the publication of our study, Liang et al published a similar study …”

Section: Visible-light-driven and Cu-catalyzed Stereoselective C(sp3)...mentioning

confidence: 57%

“…After the publication of our study, Liang et al published a similar study. 46 Because of their unique electronic properties and structural characteristics, alkylnitriles are very important in various fields. Cyanoalkyl groups incorporated into amino acids and peptides are particularly interesting due to their distinctive bioactivities, which offer potential applications in therapeutics.…”

Section: Visible-light-driven and Cu-catalyzed Stereoselective C(sp 3...mentioning

confidence: 99%

See 1 more Smart Citation

Photoinduced C(sp³)–H Functionalization of Glycine Derivatives: Preparation of Unnatural α-Amino Acids and Late-Stage Modification of Peptides

Wang

et al. 2023

Acc. Chem. Res.

View full text Add to dashboard Cite

Metrics & MoreArticle Recommendations CONSPECTUS: Peptides are essential components of living systems and contribute to critical biological processes, such as cell proliferation, immune defense, tumor formation, and differentiation. Therefore, peptides have attracted considerable attention as targets for the development of therapeutic products. The incorporation of unnatural amino acid residues into peptides can considerably impact peptide immunogenicity, toxicity, side effects, water solubility, action duration, and distribution and enhance the peptides' druggability. Typically, the direct modification of natural amino acids is a practical and effective approach for promptly obtaining unnatural amino acids. However, selective functionalization of multiple C(sp 3 )−H bonds with comparable chemical reactivities in the peptide side chains remains a formidable challenge. Furthermore, chemical modifications aimed at highly reactive (nucleophilic and aromatic) groups on peptide side chains can interfere with the biological activity of peptides.In recent years, the rapid advancement of photoinduced radical reactions has made photoredox radical−radical cross-coupling a practical approach for constructing C(sp 3 )−C(sp 3 ) bonds under mild conditions. Glycine, a naturally occurring amino acid and the fundamental skeleton of all α-amino acids, provides a basis for the alkylated modification of its own α-C(sp 3 )−H bond under mild conditions. This Account describes our recent research endeavors for systematically investigating the photocatalytic α-C(sp 3 )−H alkylation of glycine derivatives via radical−radical coupling between N-aryl glycinate-derived radicals and various alkyl radicals. In 2018, we disclosed the photoinduced Cu-catalyzed decarboxylative α-C(sp 3 )−H alkylation of glycine derivatives. Subsequently, we developed a catalyst-free method for alkylating glycine derivatives and glycine residues in peptides via electron donor−acceptor (EDA)-complex-promoted single electron transfer. Moreover, we developed a photoinduced method for the radical alkylation of Naryl glycinate α-C(sp 3 )−H bonds using unactivated alkyl chlorides (iodides) under photocatalyst-free conditions. Notably, by building on racemic alkylations of glycine derivatives and glycine-residue-containing peptides, we recently stereoselectively alkylated the N-aryl glycinate α-C(sp 3 )−H bond using a dual-functional Cu catalyst generated in situ for synthesizing a series of unnatural chiral α-amino and C-glycoamino acids.We have developed a series of methods for synthesizing unnatural amino acids through the α-C(sp 3 )−H alkylation of glycine derivatives using photoredox-promoted radical coupling as a key strategy. These methods are efficient and versatile and can be used for the late-stage modification of peptides in various contexts. Our work builds on the fundamental importance of glycine as the basic scaffold of all α-amino acids and highlights the potential of radical-based chemistry for developing chemical transformations in peptide synthesis. T...

show abstract

Section: Visible-light-driven and Cu-catalyzed Stereoselective C(sp3)...mentioning

confidence: 57%

Section: Visible-light-driven and Cu-catalyzed Stereoselective C(sp 3...mentioning

confidence: 99%

Photoinduced C(sp³)–H Functionalization of Glycine Derivatives: Preparation of Unnatural α-Amino Acids and Late-Stage Modification of Peptides

Wang

et al. 2023

Acc. Chem. Res.

View full text Add to dashboard Cite

show abstract

“…Delightfully, water and ethanol were both applicable, and ethanol provided a comparative reaction efficiency with DMSO (entries 10, 11). This result broke the limitation of alcohol solvents in the visible light-driven α-C(sp 3 )–H bond alkylation of glycine derivatives, − leaving an infinite space to enhance the reaction sustainability and workup simplicity. The screening of light sources revealed that the changes in light wavelength all led to a decrease in reaction efficiency (entries 15–17).…”

Section: Resultsmentioning

confidence: 99%

“…(2) The catalyst (2D-COF-4) was easily reused, maintaining the catalytic activity even after 10 recycle runs with unfaded basic structure and micro appearance. (3) The reaction is compatible with a green solvent (ethanol), which has always encountered failures in previous works. − This solvent led to a straightforward scale-up and easy workup procedures for the alkylation. The desired product and byproduct are obtained quickly and efficiently with standard solvent removal and filtration.…”

Section: Introductionmentioning

confidence: 99%

Visible Light-Driven Flexible Synthesis of α-Alkylated Glycine Derivatives Catalyzed by Reusable Covalent Organic Frameworks

Tian,

Bu,

Wang

et al. 2024

J. Org. Chem.

View full text Add to dashboard Cite

Herein, we report a heterogeneous visible lightdriven preparation of α-alkylated glycine derivatives. This approach employed a β-ketoenamine-linked covalent organic framework (2D-COF-4) as the heterogeneous photocatalyst and N-hydroxy phthalimide (NHPI) esters as the alkyl radical sources. Numerous glycine derivatives, including dipeptides, were precisely and efficiently alkylated under visible light-driven reaction conditions. Based on the excellent photoactivity and organic reaction compatibility of 2D-COF-4, this alkylation could proceed flexibly in a green solvent (ethanol) without any other additives. The photocatalyst and phthalimide were fruitfully recycled with a simple workup procedure, revealing a high ecoscale value and low environmental factor (E-factor).

show abstract

“…Following this, a similar study on the preparation of nonanomeric C-glycopeptides was disclosed by Liang and coworkers. [58] A recent work by Molander and co-workers also detailed a nickel-catalyzed approach for the synthesis of non-anomeric acyl C-glycosyl compounds involving the formation of an EDA complex by photoactivation. [59] Scheme 23.…”

Section: Non-anomeric Radical Glycosylationmentioning

confidence: 99%

Diversification of Glycosyl Compounds via Glycosyl Radicals

et al. 2023

View full text Add to dashboard Cite

Glycosyl radical functionalization is one of the central topics in synthetic carbohydrate chemistry. Recent advances in metal‐catalyzed cross‐coupling chemistry and metallaphotoredox catalysis provided powerful platforms for glycosyl radical diversification. In particular, the discovery of new glycosyl radical precursors in conjunction with these advanced reaction technologies have significantly expanded the space for glycosyl compound synthesis. In this Review, we highlight the most recent progress in this area starting from 2021, and the reports included will be categorized based on different reaction types for better clarity.

show abstract

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

Cited by 21 publications

References 42 publications

Photoinduced C(sp³)–H Functionalization of Glycine Derivatives: Preparation of Unnatural α-Amino Acids and Late-Stage Modification of Peptides

Photoinduced C(sp³)–H Functionalization of Glycine Derivatives: Preparation of Unnatural α-Amino Acids and Late-Stage Modification of Peptides

Visible Light-Driven Flexible Synthesis of α-Alkylated Glycine Derivatives Catalyzed by Reusable Covalent Organic Frameworks

Diversification of Glycosyl Compounds via Glycosyl Radicals

Contact Info

Product

Resources

About

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

Cited by 21 publications

References 42 publications

Photoinduced C(sp3)–H Functionalization of Glycine Derivatives: Preparation of Unnatural α-Amino Acids and Late-Stage Modification of Peptides

Photoinduced C(sp3)–H Functionalization of Glycine Derivatives: Preparation of Unnatural α-Amino Acids and Late-Stage Modification of Peptides

Visible Light-Driven Flexible Synthesis of α-Alkylated Glycine Derivatives Catalyzed by Reusable Covalent Organic Frameworks

Diversification of Glycosyl Compounds via Glycosyl Radicals

Contact Info

Product

Resources

About

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

Photoinduced C(sp³)–H Functionalization of Glycine Derivatives: Preparation of Unnatural α-Amino Acids and Late-Stage Modification of Peptides

Photoinduced C(sp³)–H Functionalization of Glycine Derivatives: Preparation of Unnatural α-Amino Acids and Late-Stage Modification of Peptides