Transformations of carbohydrate derivatives enabled by photocatalysis and visible light photochemistry

Gorelik, Daniel J.; Desai, Shrey P.; Jdanova, Sofia; Turner, Julia A.; Taylor, Mark S.

doi:10.1039/d3sc05400d

Cited by 6 publications

(1 citation statement)

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“…Effective strategies for carbohydrate functionalizations are highly desirable because of the versatile biological activities of saccharides and their derivatives. 1 While the manipulation of anomeric positions of glycosylation reactions has achieved great success, 2 C–H functionalizations of carbohydrates, offering great potential for editing sugar skeletons, are still limited. 3 Because of multiple C–H bonds with similar reactivity in monosaccharide-based molecules, the control of selectivity in C–H modifications to access diverse sugar derivatives is challenging.…”

Section: Introductionmentioning

confidence: 99%

Origin of site-selectivity of hydrogen atom transfer in carbohydrate C–H alkylations via photoredox catalysis

Ji,

Hu,

Gao

et al. 2024

Org. Chem. Front.

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Section: Introductionmentioning

confidence: 99%

Origin of site-selectivity of hydrogen atom transfer in carbohydrate C–H alkylations via photoredox catalysis

Ji,

Hu,

Gao

et al. 2024

Org. Chem. Front.

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Emerging Advances of the Radical Pathway Glycosylation Enabled by Bench‐Stable Glycosyl Donors: Glycosyl Sulfoxides, Glycosyl Sulfones, and Glycosyl Sulfinates

Dubey,

Azeem,

Mandal

2024

Adv Synth Catal

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Abstract. In synthetic carbohydrate chemistry, the modification of glycosyl radicals pathway stands as a central area of focus. The radical‐based reactions often demonstrate remarkable compatibility with various functional groups owing to the mild initiation conditions. In particular, the identification of novel glycosyl radical precursors, combined with advanced reaction techniques, has substantially broadened the scope of glycosyl compound synthesis. Despite the presence of versatile donors, the synthesis of noble donors is still addressed as a synthetic need and challenges associated with sugar chemistry. Currently, a new class of glycosyl radical precursors has been developed which enables the production of C‐, S‐, O‐, and N‐glycosides efficiently. In this light, we highlight strategies towards bench‐stable glycosyl sulfoxides, sulphone, and sulfite donors that can enable the site‐, regio‐ and stereoselective transformation of protected or naked sugar synthons in synthetic carbohydrate chemistry. Here, this review article covers the recent developments in the selective glycosyl radical diversification such as glycosyl alkylation, arylation, alkenylation, sulfuration, C‐H activation, and DNA conjugation via the bench‐stable donors along with mechanistic aspects, challenges, and future directions. 1. Introduction 2. Generation of glycosyl radical from glycosyl sulfoxide, glycosyl sulfone, and glycosyl sulfinate 3. Glycosyl radicals and the stereoselectivity 4. Early history of glycosyl sulfoxides, sulfones, and sulfinate donors 5. Generation of glycosyl radicals from glycosyl sulfoxides 6. Generation of glycosyl radicals from glycosyl sulfones 6.1 Allyl glycosyl sulfones 6.2 Heteroaryl glycosyl sulfones 7. Generation of glycosyl radicals from glycosyl sulfinates 8. Summary and Outlook

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Stereoselective Entry into α,α’‐C‐Oxepane Scaffolds through a Chalcogen Bonding Catalyzed Strain‐Release C‐Septanosylation Strategy

Ma,

Schmidt,

Strohmann

et al. 2024

Angewandte Chemie

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The utility of unconventional noncovalent interactions (NCIs) such as chalcogen bonding has lately emerged as a robust platform to access synthetically difficult glycosides stereoselectively. Herein, we disclose the versatility of a phosphonochalcogenide (PCH) catalyst to facilitate access into the challenging, but biologically interesting 7‐membered ring α,α’‐C‐disubstituted oxepane core through an α‐selective strain‐release C‐glycosylation. Methodically, this strategy represents a switch from more common but entropically less desired macrocyclizations to a thermodynamically favored ring‐expansion approach. In light of the general lack of stereoselective methods to access C‐septanosides, a remarkable palette of silyl‐based nucleophiles can be reliably employed in our method. This include a broad variety of useful synthons, such as easily available silyl‐allyl, silyl‐enol ether, silyl‐ketene acetal, vinylogous silyl‐ketene acetal, silyl‐alkyne and silylazide reagents. Mechanistic investigations suggest that a mechanistic shift towards an intramolecular aglycone transposition involving a pentacoordinate silicon intermediate is likely responsible in steering the stereoselectivity.

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Transformations of carbohydrate derivatives enabled by photocatalysis and visible light photochemistry

Abstract: This review article highlights the diverse ways in which recent developments in the areas of photocatalysis and visible light photochemistry are impacting synthetic carbohydrate chemistry.

Cited by 6 publications

References 185 publications

Origin of site-selectivity of hydrogen atom transfer in carbohydrate C–H alkylations via photoredox catalysis

Origin of site-selectivity of hydrogen atom transfer in carbohydrate C–H alkylations via photoredox catalysis

Emerging Advances of the Radical Pathway Glycosylation Enabled by Bench‐Stable Glycosyl Donors: Glycosyl Sulfoxides, Glycosyl Sulfones, and Glycosyl Sulfinates

Stereoselective Entry into α,α’‐C‐Oxepane Scaffolds through a Chalcogen Bonding Catalyzed Strain‐Release C‐Septanosylation Strategy

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