A Radical Activation Strategy for Versatile and Stereoselective N‐Glycosylation DOI

Wenyan Ding,

Xinyu Chen,

Zuyao Sun

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(36)

Published: June 5, 2024

Abstract Previous N‐glycosylation approaches have predominately involved acidic conditions, facing challenges of low stereoselectivity and limited scope. Herein, we introduce a radical activation strategy that enables versatile stereoselective using readily accessible glycosyl sulfinate donors under basic conditions exhibits exceptional tolerance towards various N‐aglycones containing alkyl, aryl, heteroaryl nucleobase functionalities. Preliminary mechanistic studies indicate pivotal role iodide, which orchestrates the formation from subsequent generation key intermediate, configurationally well‐defined is subsequently attacked by an N‐aglycone in stereospecific S N 2 manner to give desired N‐glycosides. An alternative route involving coupling nitrogen‐centered also proposed, affording exclusive 1,2‐ trans product. This novel approach promises broaden synthetic landscape N‐glycosides, offering powerful tool for construction complex glycosidic structures mild conditions.

Language: Английский

N-glycoside synthesis through combined copper- and photoredox-catalysed N-glycosylation of N-nucleophiles DOI
Qikai Sun,

Quanquan Wang,

Wenzhuo Qin

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(5), P. 623 - 632

Published: March 1, 2024

Language: Английский

Citations

25
Nickel-Catalyzed Hydrofluorination in Unactivated Alkenes: Regio- and Enantioselective C–F Bond Formation DOI
Changseok Lee, Minseok Kim, Seunghoon Han

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9375 - 9384

Published: March 21, 2024

Catalytic formation of a regio- and enantioselective C–F bond chiral center from readily available alkenes is crucial goal, yet it continues to pose significant challenges in organic synthesis. Here, we report the regioselective bonds facilitated by NiH catalysis coordination directing strategy that enables precise hydrofluorination both terminal internal alkenes. Notably, have optimized this methodology achieve high enantioselectivity creating aliphatic stereogenic centers especially with β,γ-alkenyl substrates, using tailored Bn-BOx ligand. Another pivotal finding our research identification (+)-nonlinear effect under conditions, allowing for even moderately enantiomerically enriched ligands. Given role fluorine pharmaceuticals synthetic materials, offers essential insights into centers, paving way efficient production valuable fluorinated compounds.

Language: Английский

Citations

12
Palladium-catalyzed Suzuki-Miyaura cross-couplings of stable glycal boronates for robust synthesis of C-1 glycals DOI Creative Commons

Anrong Chen,

Yang Han,

Rongfeng Wu

et al.

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

Published: June 19, 2024

Abstract C- 1 Glycals serve as pivotal intermediates in synthesizing diverse C -glycosyl compounds and natural products, necessitating the development of concise, efficient user-friendly methods to obtain glycosides is essential. The Suzuki-Miyaura cross-coupling glycal boronates notable for its reliability non-toxic nature, but donor stability remains a challenge. Herein, we achieve significant breakthrough by developing stable boronates, effectively overcoming issue glycal-based Suzuki–Miyaura coupling. Leveraging balanced reactivity our establish robust palladium-catalyzed reaction, facilitating formation various C( sp 2 )-C( ), 3 ) bonds under mild conditions. Notably, expand upon this achievement DNA-compatible reaction synthesize glycal-DNA conjugates. With excellent reactivity, stability, generality, ease handling, method holds promise widespread appication preparation products.

Language: Английский

Citations

8
Chromium‐Catalyzed Reductive Cross‐Coupling to Construct C−SS Bonds from Unactivated Alkyl Electrophiles DOI

Chao‐Peng Zhang,

Tian‐Zhang Wang,

Kang Wu

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(15)

Published: March 15, 2024

Abstract Low‐valent chromium catalysts are cheap and less toxic compared to other transition metal catalysts. Here in, we reported a ligand‐free chromium(III)‐catalyzed manganese reductive cross‐coupling of unactivated alkyl electrophiles, such as sulfonates chlorides, with trisulfide dioxides thiolation agents form carbon−sulfur bonds. The powerful method featured ample substrate scope wide functional group tolerance, constructing large number unsymmetrical disulfides under simple conditions.

Language: Английский

Citations

7
From Quaternary Carbon to Tertiary C(sp3)–Si and C(sp3)–Ge Bonds: Decyanative Coupling of Malononitriles with Chlorosilanes and Chlorogermanes Enabled by Ni/Ti Dual Catalysis DOI
Zi‐Hao Chen,

Yu-Qing Zheng,

Hong-Gui Huang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(21), P. 14445 - 14452

Published: May 13, 2024

Transition-metal-catalyzed C–Si/Ge cross-coupling offers promising avenues for the synthesis of organosilanes/organogermanes, yet it is fraught with long-standing challenges. A Ni/Ti-catalyzed strategy reported here, allowing use disubstituted malononitriles as tertiary C(sp3) coupling partners to couple chlorosilanes and chlorogermanes, respectively. This method enables catalytic cleavage C(sp3)–CN bond quaternary carbon followed by formation C(sp3)–Si/C(sp3)–Ge bonds from ubiquitously available starting materials. The efficiency generality are showcased a broad scope both partners, therefore holding potential synthesize structurally diverse organosilanes organogermanes that were difficult access previously.

Language: Английский

Citations

6
Electrochemical Glycosylation via Halogen-Atom-Transfer for C-Glycoside Assembly DOI Creative Commons
Jun Wu, Purushothaman Rajeshwaran,

Felix Kallert

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(15), P. 11532 - 11544

Published: July 19, 2024

Glycosyl donor activation emerged as an enabling technology for anomeric functionalization, but aimed primarily at O-glycosylation. In contrast, we herein disclose mechanistically distinct electrochemical glycosyl bromide activations via halogen-atom transfer and C-glycosylation. The radical addition to alkenes led C-alkyl glycoside synthesis under precious metal-free reaction conditions from readily available bromides. robustness of our e-XAT strategy was further mirrored by C-aryl C-acyl glycosides assembly through nickela-electrocatalysis. Our approach provides orthogonal with expedient scope, hence representing a general method direct C-glycosides assembly.

Language: Английский

Citations

6
The Progress of Reductive Coupling Reaction by Iron Catalysis DOI
Jian‐Qiang Zhao, Zhangpei Chen

The Chemical Record, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 17, 2024

Abstract The transition metal catalyzed coupling reaction has revolutionized the strategies for forging carbon‐carbon bonds. In contrast to traditional cross‐coupling methods using pre‐prepared nucleophilic organometallic reagents, reductive reactions C−C bonds formation provide some advantages. Because both partners are reduced in final products a stoichiometric amount of reductant, this approach not only avoids need use sensitive species, but also provides an orthogonal and complementary access classical reaction. Notably, feature readily available fragments, promote good step economy, exhibit high functional group tolerance unique chemoselectivity, which have propelled their increasingly popular organic synthesis. recent years, due low price, minimal toxicity, environmentally benign character, iron‐catalyzed garnered significant attention from synthetic chemists pharmacologists, especially coupling. This review aims insightful overview advances reactions, illustrate possible mechanisms.

Language: Английский

Citations

5
Polarity-Matched Initiation of Radical-Polar Crossover Reactions for the Synthesis of C-Allyl Glycosides with gem-Difluoroalkene Groups DOI

Hangping Zhu,

Qiu-Di Dang,

Yingwei Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(14), P. 10175 - 10179

Published: July 8, 2024

Herein, we disclose a general method for the assembly of

Language: Английский

Citations

4
Radical C‐Glycosylation Using Photoexcitable Unprotected Glycosyl Borate DOI
Yusuke Miyamoto, Sho Murakami, Yuto Sumida

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 23, 2024

Abstract We have developed radical C‐glycosylation using photoexcitable unprotected glycosyl borate. The direct excitation of borate under visible light irradiation enabled the generation anomeric without any photoredox catalysts. in situ generated was applicable to addition such as Giese‐type and Minisci‐type reaction introduce alkyl heteroaryl groups at position. In addition, radical–radical coupling between acyl imidazolide provided C‐glycosides.

Language: Английский

Citations

4
Pd-Catalyzed Stereospecific Glycosyl Cross-Coupling of Reversed Anomeric Stannanes for Modular Synthesis of Nonclassical C-Glycosides DOI Creative Commons
Cheng Guo-qiang, Bo Yang,

Yang Han

et al.

Precision Chemistry, Journal Year: 2024, Volume and Issue: 2(11), P. 587 - 599

Published: July 21, 2024

Nonclassical C-glycosides, distinguished by their unique glycosidic bond connection mode, represent a promising avenue for the development of carbohydrate-based drugs. However, accessibility nonclassical C-glycosides hinders broader investigations into structural features and modes action. Herein, we present first example Pd-catalyzed stereospecific glycosylation anomeric stannanes with aryl or vinyl halides. This method furnishes desired in good to excellent yields, while allowing exclusive control configuration. Of significant note is demonstration generality practicality this C-glycosylation approach across more than 50 examples, encompassing various protected unprotected saccharides, deoxy sugars, oligopeptides, complex molecules. Furthermore, biological evaluation indicates that modifications drug molecules can positively impact activity. Additionally, extensive computational studies are conducted elucidate rationale behind differences reaction reactivity, unveiling transmetalation transition state containing silver (Ag) within six-membered ring. Given its remarkable controllability, predictability, consistently high chemical selectivity stereospecificity regarding carbon Z/E configuration, outlined study offers solution longstanding challenge accessing stereocontrol.

Language: Английский

Citations

4