Borenium-Catalyzed ‘Chain Walking’ DOI
Yangjian Quan, Zheng Zhu

Synlett, Journal Year: 2025, Volume and Issue: unknown

Published: May 13, 2025

Abstract ‘Chain-walking’ chemistry, a catalytic process enabling the functionalization of remote positions in carbon chains, has traditionally relied on transition-metal catalysts to facilitate alkene isomerization and subsequent transformations. This Synpacts article reviews recent advancements hydroboration via chain-walking pathways, highlighting transition-metal-catalyzed strategies for α-, β-, terminal-selective borylation. Additionally, organoboron compounds emerging role borenium species as mimics are discussed. In particular, we highlight our work borenium-catalyzed ‘chain walking’ functionalization, where have unveiled novel metal-free ‘functionalization-then-isomerization’ strategy. 1 Introduction 2 Background 2.1 Transition-Metal-Catalyzed Remote Hydroboration 2.2 Isomerization Organoboron Compound 2.3 Borenium-Catalyzed Internal Alkenes 3 ‘Chain Walking’ 3.1 ‘Boron-Walking’ Strategy Design 3.2 Reaction Scope 3.3 Synthetic Application 3.4 Mechanistic Study 4 Summary Outlook

Language: Английский

Nickel-Catalyzed Asymmetric Homobenzylic Hydroamidation of Aryl Alkenes to Access Chiral β-Arylamides DOI
Xiang Lyu,

Eunmi Jeon,

Changhyeon Seo

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

Herein, we introduce a Ni-catalyzed asymmetric homobenzylic hydroamidation reaction that efficiently addresses the dual challenges of achieving regio- and enantioselectivity in synthesis β-(hetero)arylethylamides. By employing transposed NiH catalysis approach, this method facilitates formation key chiral nickel-amido intermediates, enabling insertion into alkenes to produce desired β-arylamide products with excellent enantioselectivity. The exhibits high functional group tolerance utilizes readily available starting materials vinylarenes react dioxazolone as robust amidating source. Notably, approach was successfully applied pharmaceutical compounds natural products, such Clobenzorex, Direx, Selegiline, Sacubitril, Cipargamin.

Language: Английский

Citations

0
Nickel-Catalyzed Branched Hydroalkylation of Alkenes with Diazo Compounds DOI

Nikita Kvasovs,

Valeriia Iziumchenko, Alistair J. Sterling

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

A nickel-catalyzed, branched-selective hydroalkylation of alkenes using diazo compounds has been developed. This protocol enables the functionalization both activated and unactivated alkenes, in directed nondirected manners. Mono-, di-, trisubstituted can be effectively transformed. Highly diastereoselective hydroalkylations have also demonstrated. The method provides a novel approach for introducing an α-carbonyl moiety to which is currently inaccessible by existing methods. Preliminary mechanistic investigations suggest carbene-type mechanism, unusual nickel catalysis.

Language: Английский

Citations

0
Nickel-Catalyzed 1,1-Carboboration of Polysubstituted Internal Alkenes DOI
Yao Tong, Shiyang Wang, Yu Liu

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Herein, we report a nickel-catalyzed 1,1-carboboration of di- and trisubstituted alkenyl boronates through chain-walking strategy. This reaction effectively addresses the polarity-mismatch problem via ligand control, enabling coupling various carbon-based electrophiles while accommodating broad range functional groups. The approach yields diverse tetrasubstituted carbon gem-diboronate derivatives with exceptional regioselectivity. synthetic utility this method is further demonstrated concise synthesis high-value bioactive molecules.

Language: Английский

Citations

0
Iron-Catalyzed Tunable Alkene Migratory Silylation and Transposition DOI

Bohao Guo,

Yu Pu,

Ruichen Zhang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 8, 2025

The example of iron-catalyzed alkenes migratory silylation and transposition has been demonstrated, affording a tunable approach to synthesize thermodynamically stable allylsilanes internal with high efficiency regioselectivity. These reactions showcase several advantageous features, including good functional group tolerance, excellent regioselectivity, broad substrate scope, scalability gram-scale synthesis, late-stage functionalization bio-relevant molecules. Furthermore, the relay catalytic mechanism silylation, involving both iron-silyl iron-hydride intermediates, provides valuable insights into coupling reactions, opening new avenues for development novel transformations under iron catalysis.

Language: Английский

Citations

0
Borenium-Catalyzed ‘Chain Walking’ DOI
Yangjian Quan, Zheng Zhu

Synlett, Journal Year: 2025, Volume and Issue: unknown

Published: May 13, 2025

Abstract ‘Chain-walking’ chemistry, a catalytic process enabling the functionalization of remote positions in carbon chains, has traditionally relied on transition-metal catalysts to facilitate alkene isomerization and subsequent transformations. This Synpacts article reviews recent advancements hydroboration via chain-walking pathways, highlighting transition-metal-catalyzed strategies for α-, β-, terminal-selective borylation. Additionally, organoboron compounds emerging role borenium species as mimics are discussed. In particular, we highlight our work borenium-catalyzed ‘chain walking’ functionalization, where have unveiled novel metal-free ‘functionalization-then-isomerization’ strategy. 1 Introduction 2 Background 2.1 Transition-Metal-Catalyzed Remote Hydroboration 2.2 Isomerization Organoboron Compound 2.3 Borenium-Catalyzed Internal Alkenes 3 ‘Chain Walking’ 3.1 ‘Boron-Walking’ Strategy Design 3.2 Reaction Scope 3.3 Synthetic Application 3.4 Mechanistic Study 4 Summary Outlook

Language: Английский

Citations

0