Alkene Dicarbofunctionalisation via High-Valent Nickel Catalysis DOI Creative Commons
Daoming Wang,

Li‐Qin She,

Yu-Qing He

и другие.

Опубликована: Апрель 16, 2024

Great advances have been made by leveraging high-valent Pd(II)/Pd(IV) catalysis in the areas of C–H activation and alkene difunctionalisation, thus representing a powerful approach for construction carbon-carbon carbon-heteroatom bond. However, catalytic reactions involving Ni(II)/Ni(IV) are largely underdeveloped. Here we report Ni(II)-catalysed dicarbofunctionalisation unactivated alkenes via catalysis. This protocol provides highly efficient direct route towards vicinal substituted alkanes using primary, secondary, tertiary amides, as well secondary amines native directing group under redox-neutral conditions that challenging to access through conventional methods. The key success this reaction is use bulky β-diketone ligand, which could enable insertion aryl-Ni(II) species, stabilize alkyl-Ni(II) species inhibit homolytic cleavage. features group, broad substrate scope, excellent scalability. resulting Weinreb amide-derived products can be readily derivatized variety ketones aldehyde, fundamentally useful synthetic chemistry. In addition, has employed preparation several bioactive compounds, showcasing significant values our current method.

Язык: Английский

A Bimolecular Homolytic Substitution-Enabled Platform for Multicomponent Cross-Coupling of Unactivated Alkenes DOI
Fei Cong,

Guo‐Quan Sun,

Si‐Han Ye

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(15), С. 10274 - 10280

Опубликована: Апрель 3, 2024

The construction of C(sp3)–C(sp3) bonds remains one the most difficult challenges in cross-coupling chemistry. Here, we report a photoredox/nickel dual catalytic approach that enables simultaneous formation two linkages via trimolecular alkenes with alkyl halides and hypervalent iodine-based reagents. reaction harnesses bimolecular homolytic substitution (SH2) mechanism chemoselective halogen-atom transfer (XAT) to orchestrate regioselective addition electrophilic nucleophilic radicals across unactivated without need for directing auxiliary. Utility is highlighted through late-stage (fluoro)alkylation (trideutero)methylation C═C bearing different patterns, offering straightforward access drug-like molecules comprising sp3-hybridized carbon scaffolds.

Язык: Английский

Процитировано

26
Iron-catalyzed fluoroalkylative alkylsulfonylation of alkenes via radical-anion relay DOI Creative Commons
Xiaoya Hou, Hongchi Liu, Hanmin Huang

и другие.

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

Опубликована: Фев. 17, 2024

Abstract Transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides is a powerful method for upgrading commodity chemicals into densely functionalized molecules. However, super stoichiometric amounts metal reductant and the requirement installing directing group to suppress inherent β-H elimination bring great limitations this type reaction. We demonstrate herein that two different accessible via radical-anion relay Na 2 S O 4 as both sulfone-source. The together electron-shuttle catalyst crucial divert mechanistic pathway toward formation sulfone anion instead previously reported alkylmetal intermediates. Mechanistic studies allow identification carbon-centered radical sulfur-centered radical, which are in equilibrium capture or extrusion SO could be converted accelerated by iron catalysis, leading observed high chemoselectivity.

Язык: Английский

Процитировано

25
Ni- and Pd-Catalyzed Enantioselective 1,2-Dicarbofunctionalization of Alkenes DOI
Taeho Kang,

Omar Apolinar,

Keary M. Engle

и другие.

Synthesis, Год журнала: 2023, Номер 56(01), С. 1 - 15

Опубликована: Июнь 12, 2023

Abstract Catalytic enantioselective 1,2-dicarbofunctionalization (1,2-DCF) of alkenes is a powerful transformation growing importance in organic synthesis for constructing chiral building blocks, bioactive molecules, and agrochemicals. Both two- three-component context, this family reactions generates densely functionalized, structurally complex products single step. Across several distinct mechanistic pathways at play these transformations with nickel or palladium catalysts, stereocontrol can be obtained through tailored ligands. In Review we discuss the various strategies, mechanisms, catalysts that have been applied to achieve enantioinduction alkene 1,2-DCF. 1 Introduction 2 Two-Component Enantioselective 1,2-DCF via Migratory Insertion 3 Radical Capture 4 Three-Component 5 6 Miscellaneous Mechanisms 7 Conclusion

Язык: Английский

Процитировано

24
Enantioselective Directed Nickel-Catalyzed Three-Component Reductive Arylalkylation of Alkenes via the Carbometalation/Radical Cross-Coupling Sequence DOI

Zhan Dong,

Changyu Xu,

Jianchao Chang

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 4395 - 4406

Опубликована: Март 8, 2024

Asymmetric reductive three-component arylalkylation of alkenes via the radical relay method has been well established, while asymmetric migratory insertion strategy remains unexplored. We report enantioselective nickel-catalyzed cross-electrophile with aryl- and alkyl halides an integrated Heck carbometalation/radical cross-coupling sequence. This protocol employing a chiral Ni/PHOX catalytic system allows terminal internal to successfully engage exquisite control regio-, chemo-, stereoselectivity. More importantly, this undergoes regio- arylnickelation followed by Csp3–Csp3 elimination, thus exhibiting reverse regioselectivity method. Mild reaction conditions exceptional functional group tolerance facilitate method's compatibility bioactive motifs modular synthesis biologically active compounds. The experiments density theory calculations provide insights into mechanism origin stereoselectivity, hemilabile nature PHOX ligand is critical for achieving arylalkylation.

Язык: Английский

Процитировано

15
Copper-Catalyzed Selective Amino-alkoxycarbonylation of Unactivated Alkenes with CO DOI Creative Commons

Si‐Shun Yan,

Ralf Jackstell, Matthias Beller

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 17, 2025

1,2-Amino-difunctionalization reactions of alkenes allow the efficient introduction different functional groups and rapid construction valuable functionalized amines. In this respect, we report a copper-catalyzed 1,2-amino-alkoxycarbonylation unactivated with CO alkylamine precursors in presence Lewis acid additive. The novel protocol allows direct access to β-amino derivatives from easily available starting materials. presented methods feature high chemo- regioselectivities, good group tolerance, substrate scope including diverse bioactive compounds drug-like molecules. Mechanistic studies indicate that additive is key realizing umpolung addition nucleophilic aminyl radicals electron-rich alkenes, which represents an elegant activation strategy for radicals.

Язык: Английский

Процитировано

2
Ni-Catalyzed Regioselective and Site-divergent Reductive Arylalkylations of Allylic Amines DOI Creative Commons
Huan Meng, Jun-Song Jia, Pengfei Yang

и другие.

Chemical Science, Год журнала: 2025, Номер 16(10), С. 4442 - 4449

Опубликована: Янв. 1, 2025

Catalytic methods by switching the least parameters for regioselective and site-divergent transformations to construct different architectures from identical readily available starting materials are among most ideal catalytic protocols. However, associated challenge precisely control both regioselectivity site diversity renders this strategy appealing yet challenging. Herein, Ni-catalyzed cross-electrophile 1,2- 1,3-arylalkylations of N-acyl allylic amines have been developed. This reductive three-component protocol enables 1,2-arylalkylation 1,3-arylalkylation with aryl halides alkyl excellent chemo-, regio- site-selectivity, representing first example controlled migratory difunctionalization alkenes under conditions. A wide range terminal internal unactivated amines, precursors were tolerated, providing straightforward efficient access diverse C(sp3)-rich branched aliphatic materials.

Язык: Английский

Процитировано

1
Enantioselective Ni‐Catalyzed Three‐Component Dicarbofunctionalization of Alkenes DOI Open Access

Zhan Dong,

Liangliang Song, Liang‐An Chen

и другие.

ChemCatChem, Год журнала: 2023, Номер 15(18)

Опубликована: Авг. 3, 2023

Abstract Asymmetric multicomponent reactions are considered as efficient protocols for constructing complex chiral molecules because of their step‐ and atom‐economy. Nickel‐catalyzed asymmetric three‐component dicarbofunctionalization alkenes has been well developed in recent years, which is used the area total synthesis natural products late‐stage modification drugs rapid incorporation sp 3 ‐enriched carbon centers. In this concept, significant breakthroughs field summarized, together with related mechanisms. Moreover, remaining challenges potential opportunities also highlighted.

Язык: Английский

Процитировано

19
Advancing Heterogeneous Organic Synthesis With Coordination Chemistry‐Empowered Single‐Atom Catalysts DOI

Bo‐Chao Ye,

Wenhao Li, Xia Zhang

и другие.

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 18, 2024

Abstract For traditional metal complexes, intricate chemistry is required to acquire appropriate ligands for controlling the electron and steric hindrance of active centers. Comparatively, preparation single‐atom catalysts much easier with more straightforward effective accesses arrangement control The presence coordination atoms or neighboring functional on supports' surface ensures stability single‐atoms their interactions individual substantially regulate performance Therefore, collaborative interaction between surrounding environment enhances initiation reaction substrates formation transformation crucial intermediate compounds, which imparts significant catalytic efficacy, rendering them a valuable framework investigating correlation structure activity, as well mechanism in organic reactions. Herein, comprehensive overviews both homogeneous complexes reactions are provided. Additionally, reflective conjectures about advancement synthesis also proposed present reference later development.

Язык: Английский

Процитировано

9
Hydrodeuteroalkylation of Unactivated Olefins Using Thianthrenium Salts DOI
Jie Zhang,

Mengjie Jiao,

Zheng Lu

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(36)

Опубликована: Июнь 13, 2024

Isotopically labeled alkanes play a crucial role in organic and pharmaceutical chemistry. While some deuterated methylating agents are readily available, the limited accessibility of other deuteroalkyl reagents has hindered synthesis corresponding products. In this study, we introduce nickel-catalyzed system that facilitates various deuterium-labeled through hydrodeuteroalkylation d2-labeled alkyl TT salts with unactivated alkenes. Diverging from traditional reagents, thianthrenium (TT) can effectively selectively deuterium at α position chains using D

Язык: Английский

Процитировано

8
A dinuclear gold(I) complex with bis(N-heterocyclic carbene) ligands potentiated immune responses against liver cancer via ROS-driven endoplasmic reticulum stress and ferroptosis DOI

Qiuyue Lu,

Min Shan,

Jiaqi Yang

и другие.

Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 110940 - 110940

Опубликована: Фев. 1, 2025

Язык: Английский

Процитировано

1