Nickel‐Catalyzed α‐selective Hydroalkylation of Vinylarenes DOI
Jia-Wang Wang,

Qingwei Zhu,

Deguang Liu

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(47)

Опубликована: Авг. 12, 2024

Abstract C( sp 3 ) centers adjacent to (hetero) aryl groups are widely present in physiologically active molecules. Metal‐hydride‐catalyzed hydroalkylation of alkenes represents an efficient means forging )−C( bonds, boasting advantages as a wide source substrates, mild reaction conditions, and facile selectivity manipulation. Nevertheless, the vinylarenes encounters constraints terms substrate scope, necessitating employment activated alkyl halides or containing chelating groups, remains challenge. In this context, we report general nickel‐hydride‐catalyzed protocol for vinylarenes. Remarkably, system enables α‐selective both heteroaryl under extra ligand‐free condition, demonstrating excellent coupling efficiency selectivity. Furthermore, through incorporation chiral bisoxazoline ligands, have achieved regio‐ enantioselective vinylpyrroles, thereby facilitating synthesis α‐branched alkylated pyrrole derivatives.

Язык: Английский

Diversification of Glycosyl Compounds via Glycosyl Radicals DOI Creative Commons
Yi Jiang, Yijun Zhang,

Boon Chong Lee

и другие.

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

Процитировано

64
Cobalt‐Catalyzed Facial‐Selective Hydroalkylation of Cyclopropenes DOI
Zhilin Zhang, Zhen Li,

Yuantai Xu

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Май 31, 2023

Abstract Cyclopropene hydrofunctionalization has been a promising strategy for accessing multi‐substituted cyclopropanes; however, cyclopropene hydroalkylation remains underdeveloped. Herein, we report low‐valent CoH‐catalyzed facial‐selective to access cyclopropanes. This reaction exhibits broad substrate scope of alkyl halides and cyclopropenes tolerates many functional groups. Moderate‐to‐good facial‐selectivity is obtained without any directing Mechanism studies provide evidence that radicals are generated from irreversible CoH insertion responsible the facial‐selectivity. Our preliminary exploration demonstrates asymmetric can be realized conspicuous auxiliary

Язык: Английский

Процитировано

26
Diverse Synthesis of C-Glycosides by Stereoselective Ni-Catalyzed Carboboration of Glycals DOI
Mao‐Yun Lyu, Samuel A. Jacobo, M. Kevin Brown

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 18866 - 18872

Опубликована: Июль 5, 2024

C-Glycosides are important structures that common to natural products and pharmaceutical agents. Established methods for their synthesis involve the reaction of an activated anomeric carbon. In this study, we report a conceptually new approach involves stereoselective Ni-catalyzed carboboration glycals. these reactions, not only is C–C bond formed at carbon, but synthetically useful C–B also installed. Upon oxidation, differentially protected C-glycosides be formed. addition, stereospecific manipulation leads diverse C-glycosides. Finally, application method in established C-glycosides, such as C-glycosyl amino acids, well strategy make all possible diastereomers C1 C2.

Язык: Английский

Процитировано

8
Base‐Promoted Glycosylation Allows Protecting Group‐Free and Stereoselective O‐Glycosylation of Carboxylic Acids** DOI Open Access

Hao Zuo,

Chen Zhang, Yang Zhang

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(42)

Опубликована: Авг. 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.

Язык: Английский

Процитировано

18
Enantioselective synthesis of chiral α,α-dialkyl indoles and related azoles by cobalt-catalyzed hydroalkylation and regioselectivity switch DOI Creative Commons
Jiangtao Ren,

Sun Zheng,

Shuang Zhao

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Май 6, 2024

Abstract General, catalytic and enantioselective construction of chiral α,α -dialkyl indoles represents an important yet challenging objective to be developed. Herein we describe a cobalt catalyzed anti- Markovnikov alkene hydroalkylation via the remote stereocontrol for synthesis other N -heterocycles. This asymmetric C(sp 3 )−C(sp ) coupling features high flexibility in introducing diverse set alkyl groups at α -position The utility this methodology has been demonstrated by late-stage functionalization drug molecules, bioactive natural products functional materials, identification class molecules exhibiting anti-apoptosis activities UVB-irradiated HaCaT cells. Ligands play vital role controlling reaction regioselectivity. Changing ligand from bi-dentate L6 tridentate L12 enables CoH-catalyzed hydroalkylation. Mechanistic studies disclose that involves migratory insertion process while MHAT process.

Язык: Английский

Процитировано

8
Enantioselective alkene hydroalkylation overcoming heteroatom constraints via cobalt catalysis DOI
Yan Li, Deguang Liu, Xiao Hu

и другие.

Nature Synthesis, Год журнала: 2024, Номер 3(9), С. 1134 - 1144

Опубликована: Июль 10, 2024

Язык: Английский

Процитировано

8
Direct Construction of C‐Alkyl Glycosides from Non‐Activated Olefins via Nickel‐Catalyzed C(sp3)─C(sp3) Coupling Reaction DOI Creative Commons
Changyue Yu,

Y. Wen Xu,

Mingjie Zeng

и другие.

Advanced Science, Год журнала: 2024, Номер 11(12)

Опубликована: Янв. 18, 2024

Among C-glycosides, C-alkyl glycosides are significant building blocks for natural products and glycopeptides. However, research on efficient construction methods remains relatively limited. Compared with Michael acceptors, non-activated olefins more challenging substrates have rarely been employed in the of C-glycosides. Here, a highly convenient approach synthesis through nickel-catalyzed C(sp

Язык: Английский

Процитировано

4
CoH-catalyzed asymmetric remote hydroalkylation of heterocyclic alkenes: a rapid approach to chiral five-membered S- and O-heterocycles DOI Creative Commons
Lingzi Zhao,

Feipeng Liu,

Yan Zhuang

и другие.

Chemical Science, Год журнала: 2024, Номер 15(23), С. 8888 - 8895

Опубликована: Янв. 1, 2024

A highly efficient method achieves precise construction of alkyl chiral centers at remote C3-positions in five-membered S/O-heterocycles via cobalt-catalyzed asymmetric hydroalkylation heterocyclic alkenes.

Язык: Английский

Процитировано

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, Zhi Yang

и другие.

Precision Chemistry, Год журнала: 2024, Номер 2(11), С. 587 - 599

Опубликована: Июль 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.

Язык: Английский

Процитировано

4
Stereoselective Construction of Multifunctional C-Glycosides Enabled by Nickel-Catalyzed Tandem Borylation/Glycosylation DOI
Xiaomei Wu, Shijia Li, Liqin Chen

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(32), С. 22413 - 22423

Опубликована: Авг. 3, 2024

Stereochemically pure saccharides have indispensable roles in fields ranging from medicinal chemistry to materials science and organic synthesis. However, the development of a simple, stereoselective, efficient glycosylation protocol access α- β-C-glycosides (particularly 2-deoxy entities) remains persistent challenge. Existing studies primarily focused on C1 modification carbohydrates transformation glycosyl radical precursors. Here, we innovate by harnessing situ generated glycosyl-Ni species achieve one-pot borylation cascade manner, which is enabled an earth-abundant nickel-catalyzed carboboration readily accessible glycals without any ligand. This work reveals potential for modular multifunctional platform facilitate simultaneous introduction C-C C-B bonds at stereogenic center saccharides, largely unexploited research area. Preliminary experimental computational indicate that endocyclic O C3 group play important stereoseclectively forging glycosidic bonds. As result, diverse range C-R (R = alkyl, aryl, alkenyl) 2-deoxygenated glycosides bearing modifiable boron groups could be rapidly made with excellent stereocontrol exhibit remarkable functional tolerance. The synthetic underscored late-stage natural products commercial drugs as well facile preparation various rare sugars, bioactive conjugates, key intermediates prorocentin, phomonol, aspergillide A.

Язык: Английский

Процитировано

4