Nickel-Catalyzed Synthesis of Silaindanes via Sequential C–H Activating 1,5-Nickel Migration and C–Si Activating 1,4-Nickel Migration DOI
Donghyeon Lee,

Ikuya Fujii,

Ryo Shintani

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 907 - 916

Published: Dec. 30, 2024

Catalytic reactions involving 1,n-metal migration provide a powerful approach for the synthesis of complex molecular skeletons from simple precursors through activation unreactive bonds. In this work, nickel-catalyzed 3,3-disubstituted 1-silaindanes, silicon analogues valuable indanes, was developed by reaction 1,5-nickel via C–H bond and 1,4-nickel C–Si activation. It found that not only enabled at remote position but also controlled regioselectivity subsequent alkene insertion. The detailed mechanism investigated conducting deuterium labeling experiments DFT calculations. results obtained here demonstrate high potential catalytic nickel migrations activations useful cyclic organosilicon compounds.

Language: Английский

Multiligand Enabled, Copper-Catalyzed Hiyama Coupling of Arylsilanes with Unactivated Secondary Alkyl Halides: Reaction Development and Mechanistic Insights DOI Creative Commons
Jiajing Zhou, Zhiqiang Zhang, Yan Cao

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A multiligand-involved Cu catalysis offers an efficient Hiyama coupling of arylsilanes with unactivated alkyl halides, where copper NHC and phenanthroline ligands were account for C(sp 2 )–Si activation )–C(sp 3 ) formation, respectively.

Language: Английский

Citations

2
Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization DOI
Xinghua Wang,

J. P. He,

Yanan Wang

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(17), P. 10192 - 10280

Published: Aug. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Language: Английский

Citations

12
Palladium-Catalyzed Enantioselective Multicomponent Cross-Coupling of Trisubstituted Olefins DOI

Wenyi Huang,

Yang Xi,

Deng Pan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16892 - 16901

Published: June 6, 2024

The development of a catalytic method for stereogenic carbon center formation holds immense significance in organic synthesis. Transition-metal-catalyzed cross-coupling reaction has been regarded as straightforward and efficient tool stereoselectively forging C–C bond. Nevertheless, the creation acyclic all-carbon quaternary-containing vicinal stereocenters remains notoriously challenging within domain chemistry despite their prominence various bioactive small molecules. Herein, we describe palladium-catalyzed asymmetric multicomponent trisubstituted alkene with aryl diazonium salts arylboronic acids to realize tertiary-quaternary centers high regio-, distereo-, enantioselectivity. Specifically, precise manipulation stereoconfiguration alkenes enables divergent stereoselective reaction, thus allowing facile construction all four enantiomers. Harnessing ligand-swap strategy involving chiral bisoxazoline an achiral fumarate individually accelerates enantioselective migratory insertion reductive elimination step process, supported by density functional theory (DFT) calculations, obviating requirement neighboring directing group internal olefin skeleton.

Language: Английский

Citations

9
Electroreduction strategy: a sustainable tool for the generation of aryl radicals DOI
Xiaoqing Xie,

Wei Zhou,

Ruchun Yang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(15), P. 4318 - 4342

Published: Jan. 1, 2024

This review primarily focuses on the generation of aryl radicals via an electroreduction strategy, and systematically elaborates synthetic applications, scope, limitations substrates.

Language: Английский

Citations

9
Merging SOMO activation with transition metal catalysis: Deoxygenative functionalization of amides to β-aryl amines DOI Creative Commons

Tian Hongjun,

Feng Jiang,

Xiaoming Wang

et al.

Science Advances, Journal Year: 2025, Volume and Issue: 11(3)

Published: Jan. 17, 2025

Singly occupied molecular orbital (SOMO) activation of in situ generated enamines has achieved great success (asymmetric) α-functionalization carbonyl compounds. However, examples on the use this mode transformations other functional groups are rare, and combination SOMO with transition metal catalysis is still less explored. In area deoxygenative functionalization amides, intermediates such as iminium ions were often to result formation α-functionalized amines. contrast, direct deoxygenation amides β-functionalized amines highly appealing yet remains scarcely investigated. Here, a arylation aryl halides was developed via multicatalysis iridium/photoredox/nickel/iridium, affording β-aryl high efficiency. The key reaction enamine synergy Ni-catalyzed arylation, which conjunction two compatible Ir-catalyzed reduction processes.

Language: Английский

Citations

1
Photoinduced nickel-catalysed enantioconvergent sp3–sp3 coupling of unactivated olefins and aziridines DOI
Liangliang Zhang, Hao Wang, Tomás G. Santiago

et al.

Nature Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: March 28, 2025

Language: Английский

Citations

1
Recent Advances on C—H Functionalization via Oxidative Electrophotocatalysis DOI

Aman Hasil,

Rui Chang,

Juntao Ye

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(3), P. 728 - 728

Published: Jan. 1, 2024

Language: Английский

Citations

8
Regio- and Enantioselective Nickel-Catalyzed Ipso- and Remote Hydroamination Utilizing Organic Azides as Amino Sources for the Synthesis of Primary Amines DOI

Shi‐Chao Wang,

Lin Liu,

Mei Duan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 23, 2024

Primary amines serve as key synthetic precursors to most other

Language: Английский

Citations

7
Regiodivergent and Enantioselective Synthesis of Cyclic Sulfones via Ligand‐Controlled Nickel‐Catalyzed Hydroalkylation DOI Creative Commons
Chao Fan, Uttam Dhawa, Deyun Qian

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: April 29, 2024

Abstract Cyclic sulfones have demonstrated important applications in drug discovery. However, the catalytic and enantioselective synthesis of chiral cyclic remains challenging. Herein, we develop nickel‐catalyzed regiodivergent hydroalkylation sulfolenes to streamline alkyl sulfones. The method has broad scope high functional group tolerance. regioselectivity can be controlled by ligands only. A neutral PYROX ligand favors C3‐alkylation whereas an anionic BOX C2‐alkylation. This control is kinetic origin as C2‐bound Ni intermediates are always thermodynamically more stable. Reactivity study a wide range relevant reveal I /Ni III cycle with II −H species resting state. regio‐ enantio‐determining step insertion this into 2‐sulfolene. work provides efficient for class organic compounds enhances mechanistic understanding Ni‐catalyzed stereoselective hydroalkylation.

Language: Английский

Citations

5
Nickel‐Catalyzed Regio‐ and Enantioselective Migratory Hydrocyanation of Internal Alkenes: Expanding the Scope to α,ω‐Diaryl Internal Alkenes DOI

Mingdong Jiao,

Jinguo Long,

Jianxi Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 25, 2024

Abstract Metal‐hydride‐catalyzed migratory functionalization of alkenes witnessed extensive development in the past few years. However, asymmetric version this reaction has remained largely underdeveloped owing to difficulty simultaneous control both regio‐ and stereoselectivity. In addition, exploring wider alkene substrate scope enable more synthetically valuable applications represents another challenge field. context, a nickel‐catalyzed hydrocyanation internal involving chain‐walking process is demonstrated. The exhibits excellent enantioselectivity, proceeds under mild conditions, delivers benzylic nitriles high yields. Even α,ω‐diaryl alkenes, which are known be one most challenging substrates type, could successfully converted desired products with good stereoselectivity by modifying electronic steric effects. Theoretical calculations suggest that η 3 ‐benzyl coordination mode aryl substituent (3,5‐(OMe) 2 C 6 H ) on diphosphite ligand key factors regulating enantioselectivity.

Language: Английский

Citations

4