Hydroalkylation of unactivated olefins with C(sp 3 )─H compounds enabled by NiH-catalyzed radical relay DOI Creative Commons

Jiang‐Ling Shi,

Youcheng Wang,

Yufeng Han

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(51)

Published: Dec. 18, 2024

The hydroalkylation reaction of olefins with alkanes is a highly desirable synthetic transformation toward the construction C(sp 3 )─C(sp ) bonds. However, such has proven to be challenging for unactivated olefins, particularly when substrates lack directing groups or acidic )─H Here, we address this challenge by merging NiH-catalyzed radical relay strategy HAT (hydrogen atom transfer) process. In catalytic system, nucleophilic alkyl generated from compound in presence promotor, which couples an metallic intermediate olefin substrate NiH catalyst form bond. Starting easily available materials, not only demonstrates wide functional group compatibility but also provides products regiodivergence and excellent enantioselectivity through effective control under mild conditions.

Language: Английский

Nickel-Catalyzed Rearranged Alkenylation of 2-Arylaziridines with Aryl Alkenes to Access Allylamines DOI
Xiangkai Kong,

Ming-Bai Gou,

Bo Li

et al.

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

Published: March 10, 2025

The transition-metal-catalyzed ring-opening functionalization of aziridines presents a promising approach for synthesizing structurally complex amines. However, the rearranged poses significant challenges. Herein, we report first alkenylation with aryl alkenes via Ni-Brønsted acid co-catalysis, leading to rapid synthesis diverse array allylamines yields reaching up 91%. Mechanistic studies suggest that reaction occurs through rearrangement aziridine generate an imine intermediate. This intermediate is subsequently captured by alkene under nickel catalysis, ultimately formation allylamines.

Language: Английский

Citations

1
Regioselective and Enantioselective Nickel-Catalyzed Intermolecular Reductive Coupling of Aliphatic Alkenes with Imines DOI

Zhihong Chen,

Li-Jie Gu,

Biao Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 14915 - 14921

Published: May 23, 2024

Unactivated aliphatic alkenes are particularly desirable as starting materials because they readily accessible in large quantities, but the enantioselective intermolecular reductive coupling of unactivated with imines is challenging. In this paper, we report a method for nickel-catalyzed reactions between and to yield chiral amines excellent enantioselectivities good linear selectivities. The reaction conditions compatible broad range alkenes, including those derived from bioactive molecules. success can be attributed use newly developed monodentate spiro phosphine ligands.

Language: Английский

Citations

7
Catalytic transformations of alkenes via nickelacycles DOI

Meng-Ying Qian,

Kai-Xiang Zhang,

Li‐Jun Xiao

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(16), P. 4602 - 4623

Published: Jan. 1, 2024

This review summarizes recent developments in nickel-catalyzed transformations of alkenes via nickelacycles, highlighting the advantages and challenges this innovative strategy.

Language: Английский

Citations

4
Nickel-Catalyzed Hydrocarbamoylation of Alkenes with Isocyanates DOI

Meng-Ying Qian,

Yuqing Wang, Qi‐Lin Zhou

et al.

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

Published: March 17, 2025

The hydrocarbamoylation of alkenes with isocyanates is a promising method for synthesizing amides. However, applying this strategy to more inert, simple alkenes, such as styrenes, α-olefins, and internal poses significant challenges. Here, we report the first nickel-catalyzed isocyanates, facilitated by triethoxysilane reduce nickelacycle intermediates. By switching ligands─including 6,6′-dimethyl-2,2′-bipyridine N-heterocyclic carbene─this efficiently produces amides from diverse array including gaseous olefins.

Language: Английский

Citations

0
Catalyst-controlled regiodivergence and stereodivergence in formal cross-[4+2] cycloadditions: The unique effect of bismuth(III) DOI
Qiumeng Hou,

Chenxi Cai,

Shuai‐Jiang Liu

et al.

Science Advances, Journal Year: 2025, Volume and Issue: 11(13)

Published: March 26, 2025

The [4+2] cycloaddition is crucial for constructing six-membered rings in pharmaceuticals and natural products. Cross-[4+2] cycloadditions offer greater product diversity than traditional diene-dienophile reactions due to multiple possible pathways. However, precise control over regio- stereoselectivity various isomers remains a great challenge. This study reports catalyst-controlled regiodivergent formal cross-cycloadditions of acyclic dienes enones, significantly enhancing access diverse pyrazole-fused spirooxindoles. Chiral phosphoric acid (CPA) catalysis enables endoselective cycloadditions, while Bi(III) with CPA ligand yields [2+4] products high stereoselectivity. A Claisen rearrangement the adduct produces exo-selective product, further increasing stereochemical enabling synthesis six stereo-isomers from single substrate set. DFT calculations reveal that reverses regioselectivity by repositioning reactants pocket stabilizing enone oxygen’s negative charge. In addition, 3as demonstrates therapeutic potential against triple-negative breast cancer, an IC 50 8.5 μM MDA-MB-453 cells.

Language: Английский

Citations

0
Modular synthesis of α-branched secondary alkylamines via visible-light-mediated carbonyl alkylative amination DOI Creative Commons
Milo A. Smith, Ryan Kang, Roopender Kumar

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14888 - 14898

Published: Jan. 1, 2024

A multicomponent method for the synthesis of α-branched secondary alkylamines is described. The provides expedited access to saturated N-heterocycles, and enables selective alkylation primary amines over cyclic amines.

Language: Английский

Citations

3
Mn(I)-Catalyzed Carbon-Skeleton Rearrangement of Tertiary Alcohol-Based Aldol Reaction with Aldehydes DOI

Yanshuo Xuan,

Can Yang, Huanfeng Jiang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(15), P. 10603 - 10613

Published: July 11, 2024

A Mn-catalyzed ligand-directed Csp

Language: Английский

Citations

1
Redox-Neutral Coupling of Allyl Alcohols with Trifluoromethyl Ketones via Synergistic Ni–Ti Bimetallic Catalysis DOI

Rong‐Hua Wang,

Bo Li,

Ming-Bai Gou

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(35), P. 7408 - 7413

Published: Aug. 26, 2024

A redox-neutral coupling of allyl alcohols with trifluoromethyl ketones has been developed via Ni–Ti bimetallic catalysis. This innovative method allows for the efficient synthesis various β-tertiary alcohol-substituted yields up to 98%. The reaction is scalable and compatible a wide range substrates, including complex bioactive molecules. Mechanistic studies suggest that rate-determining step involving β-H elimination presence Ti-based Lewis acid, as well hydroxyl group on crucial driving reactivity this transformation.

Language: Английский

Citations

1
Hydroalkylation of unactivated olefins with C(sp 3 )─H compounds enabled by NiH-catalyzed radical relay DOI Creative Commons

Jiang‐Ling Shi,

Youcheng Wang,

Yufeng Han

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(51)

Published: Dec. 18, 2024

The hydroalkylation reaction of olefins with alkanes is a highly desirable synthetic transformation toward the construction C(sp 3 )─C(sp ) bonds. However, such has proven to be challenging for unactivated olefins, particularly when substrates lack directing groups or acidic )─H Here, we address this challenge by merging NiH-catalyzed radical relay strategy HAT (hydrogen atom transfer) process. In catalytic system, nucleophilic alkyl generated from compound in presence promotor, which couples an metallic intermediate olefin substrate NiH catalyst form bond. Starting easily available materials, not only demonstrates wide functional group compatibility but also provides products regiodivergence and excellent enantioselectivity through effective control under mild conditions.

Language: Английский

Citations

0