Diversification of Glycosyl Compounds via Glycosyl Radicals

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(38)

Опубликована: Июнь 7, 2023

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

Язык: Английский

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

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5502 - 5510

Опубликована: Фев. 15, 2024

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

Язык: Английский

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Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 26, 2024

Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp

Язык: Английский

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C‐GlycosideSynthesis Enabled by Nickel Catalysis

Chinese Journal of Chemistry, Год журнала: 2023, Номер 41(17), С. 2217 - 2236

Опубликована: Апрель 13, 2023

Comprehensive Summary C‐Glycosides are critical, naturally occurring products and medicinal candidates, extensive efforts have been made to explore efficient approaches for creating C‐glycosidic bonds. Transition‐metal‐catalysis, particularly nickel‐catalyzed C‐glycosylation reactions constitute a promising strategy. However, achieving stereoselective synthesis of α‐ β‐C‐glycosides has long‐standing challenge. To address this problem, variety nickel‐mediated strategies developed. This review highlights recent developments in the diastereoselective briefly summarizes mechanistic understandings these methods.

Язык: Английский

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Recent Advances in First-Row Transition Metal-Catalyzed Reductive Coupling Reactions for π-Bond Functionalization and C-Glycosylation

Accounts of Chemical Research, Год журнала: 2023, Номер 56(22), С. 3292 - 3312

Опубликована: Ноя. 2, 2023

ConspectusEfficient construction of ubiquitous carbon-carbon bonds between two electrophiles has garnered interest in recent decades, particularly if it is mediated by nonprecious, first-row transition metals. Reductive coupling advantages over traditional cross-coupling obviating the need for stoichiometric air- and moisture-sensitive organometallic reagents. By harnessing metal-catalyzed reductive as a powerful tool, intricate molecular architectures can be readily assembled through installation C-C across π systems (alkenes/alkynes) via reaction with appropriate electrophiles. Despite advances alkene difunctionalization, there remains significant potential discovery novel pathways. In this regard, development protocols that enable union challenging alkyl/alkynyl high regio- chemoselectivity highly sought-after goal.Apart from π-bond functionalization, found application carbohydrate chemistry, synthesis valuable C-glycosyl compounds. vein, suitable glycosyl donors used to generate reactive radical intermediates under conditions. Through elaborately designed reactions, these trapped furnish pharmaceutically relevant glycoconjugates. Consequently, diversification compound using metal catalysis holds strong appeal.In Account, we summarize our efforts reactions applications alkene/alkyne functionalization C-glycosylation. We will first discuss nickel (Ni)-catalyzed difunctionalization alkenes, aided an 8-aminoquinoline (AQ) directing auxiliary. Next, highlight Ni-catalyzed hydroalkylation alkenyl amides tethered similar AQ-derived Lastly, efficient 1,3-enynes involving site- stereoselective terminal alkynes alkynyl halides NHPI esters.Beyond dicarbofunctionalization, extended paradigm toward C-glycosidic linkages carbohydrates. employing earth-abundant iron (Fe)-based catalyst, show useful radicals generated chlorides These captured bond formation C-aryl, C-alkenyl, C-alkynyl compounds diastereoselectivity. Our multicomponent chlorides, aryl/alkyl iodides, isobutyl chloroformate conditions led C-acyl glycosides. addition Fe Ni, discovered Ti-catalyzed/Mn-promoted synthetic route access C-alkyl C-alkenyl compounds, electron-deficient alkenes/alkynes. further developed electron donor-acceptor (EDA) photoactivation system leveraging decarboxylative deaminative strategies C-glycosylation Ni catalysis. This approach been demonstrated selectively activate carboxyl amino motifs glycopeptide conjugates. Finally, distinct catalytic transformations bench-stable heteroaryl sulfones, achieved stereodivergent both α- β-anomers C-aryl glycosides, one which involves aryl iodides.The findings presented Account are anticipated have far-reaching implications beyond research. foresee results pave way new founded on concept coupling, leading future.

Язык: Английский

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Three-Component Fusion to Pyrazolo[5,1-a]isoquinolines via Rh-Catalyzed Multiple Order Transformation of Enaminones

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(7), С. 4833 - 4838

Опубликована: Март 22, 2023

A facile and practical method for the synthesis of fused tricyclic pyrazolo[5,1-a]isoquinolines has been realized via reactions enaminones, hydrazine hydrochloride, internal alkynes. By means Rh catalysis, extraordinary high-order bond functionalization, including transformation aryl C–H, ketone C═O, alkenyl C–N bonds in marks major feature cascade reactions. The results disclose individual advantage enaminones design novel efficient synthetic methods.

Язык: Английский

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Nickel-Catalyzed Carbonylative Negishi Cross-Coupling of Unactivated Secondary Alkyl Electrophiles with 1 atm CO Gas

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(12), С. 7971 - 7978

Опубликована: Март 14, 2024

We describe a nickel-catalyzed carbonylative cross-coupling of unactivated secondary alkyl electrophiles with the organozinc reagent at atmospheric CO gas, thus allowing expedient construction unsymmetric dialkyl ketones broad functional group tolerance. The leverage newly developed

Язык: Английский

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Stereoselective and site-divergent synthesis of C-glycosides

Nature Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Сен. 13, 2024

Язык: Английский

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Exploiting π and Chalcogen Interactions for the β‐Selective Glycosylation of Indoles through Glycal Conformational Distortion

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(7)

Опубликована: Дек. 20, 2023

Harnessing unconventional noncovalent interactions (NCIs) is emerging as a formidable synthetic approach in difficult-to-access glycosidic chemical space. C-Glycosylation, particular, has gained flurry of recent attention. However, most reported methods are restricted to the relatively facile access α-C-glycosides. Herein, we disclose β-stereoselective glycosylation indoles by employing phosphonoselenide catalyst. The robustness this protocol exemplified its amenability for reaction at both indolyl C- and N- reactivity sites. In contrast previous reports, which chalcogens were solely involved Lewis acidic activation, our mechanistic investigation unraveled that often neglected flanking aromatic substituents phosphonoselenides can substantially contribute catalysis engaging π-interactions. Computations NMR spectroscopy indicated chalcogenic components catalyst be collectively exploited foster conformational distortion glycal away from usual half-chair boat conformation, liberates convex β-face nucleophilic attack.

Язык: Английский

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Nickel-Catalyzed Highly Selective Reductive Carbonylation Using Oxalyl Chloride as the Carbonyl Source

ACS Catalysis, Год журнала: 2023, Номер 13(12), С. 8161 - 8168

Опубликована: Июнь 2, 2023

Nickel-catalyzed carbonylative cross-electrophile coupling which emerges as a powerful, efficient, and low-cost method for constructing challenging carbonyl derivatives has attracted increasing attention of organic chemists. To avoid the generation poisonous, volatile, inert nickel complex, it is critical to develop an cheap, easily available CO surrogate. Oxalyl chloride, cheap commercially chemical, one most versatile reagents used in chemical reactions. In this work, high chemoselectivity can be achieved with 1:1:1 ratio Ar–I alkyl-I oxalyl chloride. A wide range alkyl aryl ketones present important class molecules synthetic medicinal chemistry are accessed from halides, iodides, under mild conditions. Primary secondary iodides were suitable substrates. Various functional groups well tolerated, affording up 90% yields. This protocol was also derivatization natural products drug molecules. Mechanistic investigation indicates that reaction Zn chloride conditions could release slowly. knowledge should useful further development multicomponent cross-coupling

Язык: Английский

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