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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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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Unlocking the Chain‐Walking Process in Gold Catalysis**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Oct. 2, 2023

The successful realization of gold-catalyzed chain-walking reactions, facilitated by ligand-enabled Au(I)/Au(III) redox catalysis, has been reported for the first time. This breakthrough led to development annulation reaction alkenes with iodoarenes leveraging interplay and π-activation reactivity mode. mechanism elucidated through comprehensive experimental computational studies.

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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Iridium‐Catalyzed Remote Site‐Switchable Hydroarylation of Alkenes Controlled by Ligands

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(41)

Published: Aug. 23, 2023

An iridium-catalyzed remote site-switchable hydroarylation of alkenes was reported, delivering the products functionalized at subterminal methylene and terminal methyl positions on an alkyl chain controlled by two different ligands, respectively, in good yields with to excellent site-selectivities. The catalytic system showed functional group tolerance a broad substrate scope, including unactivated activated alkenes. More importantly, regioconvergent transformations mixtures isomeric were also successfully realized. results mechanistic studies demonstrate that reaction undergoes chain-walking process give [Ar-Ir-H] complex alkene. subsequent processes proceed through modified Chalk-Harrod-type mechanism via migratory insertion alkene into Ir-C bond followed C-H reductive elimination afford hydrofunctionalization site-selectively.

Language: Английский

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Iridium-Catalyzed Migratory Terminal C(sp³)–H Amidation of Heteroatom-Substituted Internal Alkenes via Olefin Chain Walking

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: unknown

Published: Oct. 31, 2023

Hydroamination facilitated by metal hydride catalysis is an appealing synthetic approach to access valuable nitrogen-containing compounds from readily available unsaturated hydrocarbons. While high regioselectivity can be achieved usually for substrates bearing polar chelation groups, the reaction involving simple alkenes frequently provides nonselective outcomes. Herein, we report iridium-catalyzed highly regioselective terminal C(sp3)-H amidation of internal utilizing dioxazolones as amino source via olefin chain walking. Most notably, this mechanistic motif double bond migration position operates not only with dialkyl-substituted including styrenes but also heteroatom-substituted olefins such enol ethers, vinyl silanes, and borons, thus representing first example methyl latter type through a nondissociative walking process.

Language: Английский

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Rhodium(III)-Catalyzed Remote Hydroamidation of Internal Alkenes Via Chain Walking

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 16337 - 16343

Published: Dec. 6, 2023

Hydroamination of terminal alkenes represents a powerful and well-established way to introduce nitrogenous functionality feedstock chemicals. Remote hydroamination reactions are far less known represent functionalize unactivated C(sp3) centers distal the site alkene. These transformations commonly take place via metal-hydride-mediated chain walking, as such, regioselectivity can be challenging. The remote introduction amides is particular interest due their prevalence in pharmaceuticals. Herein we report Rh(III)-catalyzed hydroamidation procedure position internal alkenes, using dioxazolones amidation reagents i-PrOH hydride source. reaction proceeds with high yield tolerates variety functionality. Regioconvergent synthesis single linear amide from mixture isomeric demonstrated. Key development this was determining that inorganic bases poison catalyst identifying suitable trialkylamine replacement.

Language: Английский

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A Photo- and Cobalt-Catalyzed Highly Selective and Divergent Hydrofunctionalization of 1,3-Dienes with Phenols

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

Published: Jan. 1, 2025

An applicable cobalt-hydride-mediated selective, divergent hydroetherification and sequential hydroetherification/hydroarylation of 1,3-dienes with simple phenol feedstocks under a photoredox cobalt catalytic system have been developed. A variety allyl aryl ethers value-added chroman derivatives can be obtained in good to excellent yields stereoselectivity. This method not only obviates the need for extra hydrosilanes stoichiometric oxidants, thereby offering exceedingly mild conditions alkene hydroetherification, but also represents first case CoH-HAT-catalyzed double hydrofunctionalization alkenes sole nucleophile. The continuous selective bond-forming expands applications cobalt-hydride MHAT reaction provides novel approach design synthesis heterocyclic molecules.

Language: Английский

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Amide-Directed Rhodium-Catalyzed Chain-Walking Hydrothiolation of Internal Alkenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(12), P. 2500 - 2504

Published: March 18, 2024

We developed a rhodium-catalyzed chain-walking hydrothiolation process for internal alkenes, which offers novel and efficient alternative C(sp3)–H bond cleavage, while focusing on thiol incorporation. This method exclusively affords N,S-acetals at 36–90% yields. Regioconvergent significantly improved the effectiveness of this transformation. Preliminary mechanistic investigations revealed that an amide-directing group is essential regioselective synthesis, underlining its significance in process.

Language: Английский

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Diphosphine Ligand‐Enabled Nickel‐Catalyzed Chelate‐Assisted Inner‐Selective Migratory Hydroarylation of Alkenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 21, 2023

The precise control of the regioselectivity in transition metal-catalyzed migratory hydrofunctionalization alkenes remains a big challenge. With transient ketimine directing group, nickel-catalyzed β-selective hydroarylation and hydroalkenylation alkenyl ketones has been realized with aryl boronic acids using alkyl halide as mild hydride source for first time. key to this success is use diphosphine ligand, which capable generation Ni(II)-H species presence bromide, enabling efficient insertion alkene into sequent rapid chain walking process. present approach diminishes organosilanes reductant, tolerates wide array complex functionalities excellent regioselective control. Moreover, catalytic system could also be applied azahetereoarenes, thus providing general preparation 1,2-aryl heteroaryl motifs potential applications pharmaceutical discovery.

Language: Английский

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