C‐GlycosideSynthesis Enabled by Nickel Catalysis

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(17), P. 2217 - 2236

Published: April 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.

Language: Английский

---

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

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(22), P. 3292 - 3312

Published: Nov. 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.

Language: Английский

---

Recent advances on synthesis of C-glycosides

Carbohydrate Research, Journal Year: 2023, Volume and Issue: 530, P. 108856 - 108856

Published: June 5, 2023

Language: Английский

---

Dehydroxylative radical N-glycosylation of heterocycles with 1-hydroxycarbohydrates enabled by copper metallaphotoredox catalysis

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: April 22, 2024

Abstract N-Glycosylated heterocycles play important roles in biological systems and drug development. The synthesis of these compounds heavily relies on ionic N-glycosylation, which is usually constrained by factors such as labile glycosyl donors, precious metal catalysts, stringent conditions. Herein, we report a dehydroxylative radical method for synthesizing N -glycosides leveraging copper metallaphotoredox catalysis, stable readily available 1-hydroxy carbohydrates are activated direct N-glycosylation. Our employs inexpensive photo- copper- catalysts can tolerate some extent water. reaction exhibits broad substrate scope, encompassing 76 examples, demonstrates high stereoselectivity, favoring 1,2- trans selectivity furanoses α-selectivity pyranoses. It also site-selectivity substrates containing multiple N-atoms. synthetic utility showcased through the late-stage functionalization bioactive pharmaceuticals like Olaparib, Axitinib, Metaxalone. Mechanistic studies prove presence radicals importance catalysis.

Language: Английский

---

Linkage-Editing Pseudo-Glycans: A Reductive α-Fluorovinyl-C-Glycosylation Strategy to Create Glycan Analogs with Altered Biological Activities

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(3), P. 2237 - 2247

Published: Jan. 10, 2024

The acetal (O-glycoside) bonds of glycans and glycoconjugates are chemically biologically vulnerable, therefore C-glycosides interest as more stable analogs. We hypothesized that, if the O-glycoside linkage plays a vital role in glycan function, biological activities C-glycoside analogs would vary depending on their substituents. Based this idea, we adopted "linkage-editing strategy" for creation (pseudo-glycans). designed three types pseudo-glycans with CH2 CHF linkages, which resemble terms bond lengths, angles, bulkiness, synthesized them efficiently by means fluorovinyl C-glycosylation selective hydrogenation reactions. Application strategy to isomaltose (IM), an inducer amylase expression, α-GalCer, activates iNKT cells, resulted discovery CH2-IM, shows increased production ability, CHF-α-GalCer, activity opposite that native serving antagonist cells.

Language: Английский

---

Stereoselective and site-divergent synthesis of C-glycosides

Nature Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

Language: Английский

---

Catalytic Multicomponent Synthesis ofC‐Acyl Glycosides by Consecutive Cross‐Electrophile Couplings

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(46)

Published: Sept. 27, 2022

C-Acyl glycosides are versatile intermediates to natural products and medicinally relevant entities. Conventional cross-coupling strategies secure these molecules often relied on two-component manifolds in which a glycosyl precursor is coupled with an acyl donor (pre-synthesized or generated situ) under transition metal dual catalysis forge C-C bond. Here, we disclose three-component Ni-catalyzed reductive regime that facilitates the chemoselective union of halides, organoiodides commercially available isobutyl chloroformate as CO surrogate. The method tolerates multiple functionalities resulting obtained high diastereoselectivities. Theoretical calculations provide mechanistic rationale for unexpectedly chemoselectivity sequential cross-electrophile couplings. This approach enables expeditious assembly difficult-to-synthesize C-acyl glycosides, well late-stage keto-glycosylation oligopeptides.

Language: Английский

---

Recent Progress in Transition-Metal-Catalyzed Reductive Cross-Coupling Reactions Using Diboron Reagents as Reductants

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(23), P. 15469 - 15480

Published: Nov. 16, 2023

Transition-metal-catalyzed reductive cross-coupling reactions have been developed as one of the important tools for constructing C–C bonds. These involve direct coupling two distinct electrophiles promoted by transition metals and reductants. Notably, these methods offer advantages over conventional because they circumvent need air- moisture-sensitive organometallic reagents while being simple to operate exhibiting good compatibility with various functional groups. In recent years, diboron gained prominence reductants alongside traditional metal reductants, such Zn, Mn, Mg. This Review aims provide an insightful overview nickel/copper/iron-catalyzed using illustrate their possible reaction mechanisms.

Language: Английский

---

Base‐Promoted Glycosylation Allows Protecting Group‐Free and Stereoselective O‐Glycosylation of Carboxylic Acids**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(42)

Published: Aug. 17, 2023

Here we report a simple and general method to achieve fully unprotected, stereoselective glycosylation of carboxylic acids, employing bench-stable allyl glycosyl sulfones as donors. Running the reaction under basic conditions was crucial for efficiencies selectivities. Both donor activation stage glycosidic bond forming process are compatible with free hydroxyl groups, thereby allowing use unprotected This transformation is stereoconvergent, occurs mild metal-free at ambient temperature visible light (455 nm) irradiation, displays remarkable scope respect both partners. Many natural products commercial drugs, including an acid derived from complex anticancer agent taxol, were efficiently glycosylated. Experimental studies provide insights into origin stereochemical outcome.

Language: Английский

---

Catalytic cross-electrophile coupling of aryl chlorides with unactivated alkyl chlorides: The synergy of iron and Li

Chem, Journal Year: 2023, Volume and Issue: 9(12), P. 3623 - 3636

Published: Sept. 5, 2023

Language: Английский

---