Access to Enantioenriched 1,n-Diamines via Ni-Catalyzed Hydroamination of Unactivated Alkenes with Weakly Coordinating Groups

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(15), P. 9638 - 9645

Published: July 25, 2022

Enantioenriched 1,2- and 1,3-diamines with chiral α-branched aliphatic amine motifs are important substructures in bioactive compounds related molecules serve as privileged ligands both organo- transition-metal-catalysis. However, direct access to such structural remains a formidable challenge. Herein, straightforward method 1,n-diamines (n = 2, 3, 4) containing is achieved by Ni-catalyzed asymmetric hydroamination of unactivated alkenes. Facilitated remote weakly coordinating group, the reaction applicable terminal internal alkenes, delivering enantioenriched 1,2-, 1,3-, 1,4-diamine precursors good yields excellent enantioselectivities diverse substitution patterns. Unactivated alkenes secondary alkyl nucleophile surrogates presence Ni–H, forging C–N bond enantioselectively aminating reagents. In addition, proceeds at room temperature functional group tolerance.

Language: Английский

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Intramolecular hydroamidation of alkenes enabling asymmetric synthesis of β-lactams via transposed NiH catalysis

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(9), P. 784 - 795

Published: Aug. 24, 2023

Language: Английский

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Ligand-Controlled NiH-Catalyzed Regiodivergent and Enantioselective Hydroamination of Alkenyl Amides

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(15), P. 10041 - 10047

Published: July 18, 2023

Transition-metal-catalyzed remote hydrofunctionalization of alkenes remains an efficient but challenging protocol in chemical synthesis. Herein, we reported a ligand-controlled, directing-group-assisted strategy to promote NiH-catalyzed site-selective (α, β, or γ) hydroamination unactivated with weakly coordinating amide groups. The key success lies the employment proper yet commercially available bidentate nitrogen-containing ligands, which enables delivery 1,1-, 1,2-, and 1,3-diamines good-to-excellent regioselectivity starting from same substrates. A broad range O-benzoylhydroxylamine electrophiles different functional groups can be installed via Ni migration nonmigration. Moreover, these predicable positionally selective protocols provide method for enantioselective synthesis highly valued 1,2-diamines (via aliphatic C–H amination) 1,3-diamines.

Language: Английский

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Silanes as a versatile hydride source for Ni–H catalysis: a promising tool for π-hydro functionalization

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(15), P. 4290 - 4317

Published: Jan. 1, 2024

Nickel-catalyzed hydrofunctionalization of π-substrates is a possibly effective method to synthesize several value-added molecular architectures. This review covers the NiH catalyzed reactions alkenes, alkynes and allenes.

Language: Английский

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

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

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Nickel‐Catalyzed Kinetic Resolution of Racemic Unactivated Alkenes via Enantio‐, Diastereo‐, and Regioselective Hydroamination

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)

Published: April 20, 2023

Abstract Kinetic resolution is a powerful strategy for the isolation of enantioenriched compounds from racemic mixtures, and development selective catalytic processes an active area research. Here, we present nickel‐catalyzed kinetic α‐substituted unconjugated carbonyl alkenes via enantio‐, diastereo‐, regioselective hydroamination. This protocol affords both chiral butenamides syn ‐β 2,3 ‐amino acid derivatives with high enantiomeric purity (up to 99 % ee) selectivity factor up >684. The key excellent efficiency distinctive architecture nickel complex, which enables successful enantioselective C−N bond construction. Mechanistic investigations reveal that unique structure ligand facilitates rapid migratory insertion step one enantiomer. provides practical versatile approach prepare wide range compounds.

Language: Английский

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Palladium‐Catalyzed Enantioselective Hydrofunctionalization of Alkenes: Recent Advances

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(43)

Published: Sept. 8, 2023

Abstract Palladium‐catalyzed asymmetric hydrofunctionalization of alkenes is one the most powerful and straightforward methods to forge a new C−H bond C−X (X=C, N, O, F, Si etc) bond, which provides an efficient way obtain valuable enantioenriched molecules from cheap readily available feedstocks. Catalytic simple challenging but still highly sought after. This review will mainly focus on recent advances in Palladium catalyzed over past decade, including hydroamination, hydrooxygenation, hydrofluorination, hydrosilylation, hydroarylation, hydroalkenylation hydrocarbonylation.

Language: Английский

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P,N Ligand in Ni-Catalyzed Cross-Coupling Reactions: A Promising Tool for π-Functionalization

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(20), P. 13540 - 13560

Published: Oct. 6, 2023

Bidentate P,N ligands, integrating phosphine and nitrogen donors, are highlighted for their versatile characteristics, offering both electronic steric tunability. Their hemilabile nature, coupled with the ability to modulate properties through choice of donor atoms substituents, has expanded horizons chemical transformations. This Review focuses on Ni-catalyzed cross-coupling reactions mediated by ligands. The asymmetrical nature each atom playing a specific role in catalytic cycle, offers control, stability, unique regioselectivity processes. In particular, Ni/P,N-catalytic system exhibits remarkable reactivity π-substrates including alkenes, alkynes, allenes. A thorough mechanistic understanding these processes insights into trends future directions Ni/P,N-catalyzed reactions.

Language: Английский

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NiH-catalyzed C–N bond formation: insights and advancements in hydroamination of unsaturated hydrocarbons

Chemical Science, Journal Year: 2023, Volume and Issue: 15(2), P. 442 - 457

Published: Dec. 6, 2023

The formation of C-N bonds is a fundamental aspect organic synthesis, and hydroamination has emerged as pivotal strategy for the synthesis essential amine derivatives. In recent years, there been surge interest in metal hydride-catalyzed reactions common alkenes alkynes. This method avoids need stoichiometric organometallic reagents overcomes problems associated with specific compounds that may impact functional group compatibility. Notably, developments have brought to forefront olefinic hydroamidation facilitated by nickel hydride (NiH) catalysis. inclusion suitable chiral ligands paved way realization asymmetric realm olefins. review aims provide an in-depth exploration latest achievements bond through intermolecular catalyzed hydrides. Leveraging this innovative approach, diverse range alkene alkyne substrates can be efficiently transformed into value-added enriched bonds. intricacies are succinctly elucidated, offering concise overview underlying reaction mechanisms. It our aspiration comprehensive will stimulate further progress NiH-catalytic techniques, fine-tune systems, drive innovation catalyst design, foster deeper understanding

Language: Английский

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Recent Progress in NiH-Catalyzed Linear or Branch Hydrofunctionalization of Terminal or Internal Alkenes

Topics in Current Chemistry, Journal Year: 2023, Volume and Issue: 381(5)

Published: July 20, 2023

Language: Английский

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