Modulable Photocatalyzed Strategies for the Synthesis of α-<i>C</i>-Glycosyl Alanine Analogues via the Giese Reaction with Dehydroalanine Derivates

Poletti, Lorenzo; Massi, Alessandro; Ragno, Daniele; Droghetti, Federico; Natali, Mirco; Risi, Carmela De; Bortolini, Olga; Carmine, Graziano Di

doi:10.1021/acs.orglett.3c01660

Cited by 7 publications

(2 citation statements)

References 36 publications

(56 reference statements)

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“…This same approach was utilized by the Di Carmine group to perform an α-selective Giese reaction between dehydroalanine derivatives 25 and pyranosyl/furanosyl bromides 26 for the generation of α-C-glycosyl alanines 27 (Scheme 7). [21] Similarly, Leonori reported an allylation reaction using electrophilic allyl reagents (Scheme 8), [10] which emulates the products of an electrophilic cross-coupling between allyl halides 28 and alkyl halides 29, affords products 30 in moderate to good yields (Scheme 8). In this case, Leonori proposed that the chlorine radical 33, generated after radical addition of alkyl radical 31 to the allyl chloride 28, is responsible for the oxidation and regeneration of the 4CzIPN photocatalyst.…”

Section: C(sp 3 )-C(sp 3 ) Bond Formationmentioning

confidence: 99%

An Overview of α‐Aminoalkyl Radical Mediated Halogen‐Atom Transfer

2023

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The merging of photocatalysis with halogen‐atom transfer (XAT) processes has proven to be a versatile tool for the generation of carbon‐centered radicals in organic synthesis. XAT processes are unique in that they generate radicals without requiring the use of strong reductants necessary for the traditional single electron transfer (SET) activation of halides. Pathways to achieve XAT in synthetic applications can be categorized into three major sections: i) heteroatom‐based activators, ii) metal‐based activators, and iii) carbon‐based activators among which α‐aminoalkyl radicals have taken the center stage. Access to these α‐aminoalkyl radicals as XAT reagents has gained significant attention in the past few years due to the robustness of the reactions, the simplicity of the reagents required, and the broadness of their applications. Generation of these α‐aminoalkyl radicals is simply achieved through the single electron oxidation of tertiary amines, which after deprotonation at the α‐position generates the α‐aminoalkyl radicals. Due to the wide scope of tertiary amines available and the tunable nucleophilicity of α‐aminoalkyl radical formed, this strategy has become an attractive alternative to heteroatom/metal‐based radicals for XAT. In this minireview, we focus our attention on recent (2020‐2023) developments and uses of this robust technology to mediate XAT processes.

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Section: C(sp 3 )-C(sp 3 ) Bond Formationmentioning

confidence: 99%

An Overview of α‐Aminoalkyl Radical Mediated Halogen‐Atom Transfer

2023

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“…Current methods for synthesizing C -glycopeptides involve the implementation of Giese-type reactions, − where sugar radicals are trapped by electron-deficient alkenes, forming C -glycopeptides with saturated sp 3 carbon linkages. The Yu group disclosed Ni-catalyzed reductive hydroglycosylation to prepare vinyl C -glycosyl amino acids and peptides .…”

Section: Introductionmentioning

confidence: 99%

Direct Formation of Amide-Linked C-Glycosyl Amino Acids and Peptides via Photoredox/Nickel Dual Catalysis

Ye,

Wang,

Jin

et al. 2024

J. Am. Chem. Soc.

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Glycoproteins account for numerous biological processes including those associated with diseases and infections. The advancement of glycopeptides has emerged as a promising strategy for unraveling biological pathways and discovering novel medicines. In this arena, a key challenge arises from the absence of efficient synthetic strategies to access glycopeptides and glycoproteins. Here, we present a highly concise approach to bridging saccharides with amino acids and peptides through an amide linkage. Our amide-linked C-glycosyl amino acids and peptides are synthesized through cooperative Ni-catalyzed and photoredox processes. The catalytic process generates a glycosyl radical and an amide carbonyl radical, which subsequently combine to yield the C-glycosyl products. The saccharide reaction partners encompass mono-, di-, and trisaccharides. All 20 natural amino acids, peptides, and their derivatives can efficiently undergo glycosylations with yields ranging from acceptable to high, demonstrating excellent stereoselectivities. As a substantial expansion of applications, we have shown that simple C-glycosyl amino acids can function as versatile building units for constructing Cglycopeptides with intricate spatial complexities.

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Photoredox-catalyzed C-glycosylation of peptides with glycosyl bromides

Li,

Zhao,

2024

Chinese Chemical Letters

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Modulable Photocatalyzed Strategies for the Synthesis of α-C-Glycosyl Alanine Analogues via the Giese Reaction with Dehydroalanine Derivates

Cited by 7 publications

References 36 publications

An Overview of α‐Aminoalkyl Radical Mediated Halogen‐Atom Transfer

An Overview of α‐Aminoalkyl Radical Mediated Halogen‐Atom Transfer

Direct Formation of Amide-Linked C-Glycosyl Amino Acids and Peptides via Photoredox/Nickel Dual Catalysis

Photoredox-catalyzed C-glycosylation of peptides with glycosyl bromides

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