Development of Earth-Abundant Metals-Catalyzed Enantioselective Alkenylations Using Alkenyl Metal Reagents

Wu, Liang; Wei, Hanlin; Shen, Jiefeng; Chen, Jianzhong; Zhang, Wanbin

doi:10.6023/a21070338

Cited by 13 publications

(3 citation statements)

References 186 publications

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“…Catalytic enantioselective alkylation and arylation of Michael acceptors are important C–C bond forming transformations in organic synthesis . They have been widely applied in syntheses of natural products and medicines . Different from catalytic alkylation and arylation, analogous alkenylation gives products containing olefinic fragments, which are readily converted to a plethora of functionalized aliphatic groups and thus significantly widen chemical space available.…”

Section: Introductionmentioning

confidence: 99%

“…They have been widely applied in syntheses of natural products and medicines . Different from catalytic alkylation and arylation, analogous alkenylation gives products containing olefinic fragments, which are readily converted to a plethora of functionalized aliphatic groups and thus significantly widen chemical space available. On the other hand, the reactivity and stereoselectivity in catalytic alkenyl-transfer reactions are highly susceptible to steric and electronic perturbation of olefinic substituents, which often poses as a challenge in developing alkenylation methods with a rather general scope.…”

Section: Introductionmentioning

confidence: 99%

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Enantioselective Reductive Conjugate Alkenylation of α,β-Unsaturated Ketones and Amides via Nickel Catalysis

Zhao,

Zhang,

Zhou

2024

ACS Catal.

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Chiral nickel complexes promoted enantioselective reductive alkenylation of a range of conjugated enones, using alkenyl bromides, triflates, and tosylates. The neutral condition was compatible with sensitive groups and azaheteroaryl rings. Importantly, alkenyl groups in products can be readily converted to functionalized alkyl groups via iron-catalyzed reductive hydrofunctionalization. Some examples of asymmetric alkenylation of N-enoyl pyrroles and indoles were also included.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Enantioselective Reductive Conjugate Alkenylation of α,β-Unsaturated Ketones and Amides via Nickel Catalysis

Zhao,

Zhang,

Zhou

2024

ACS Catal.

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“…Efficiency and selectivity are two core issues in organic synthesis. Developing efficient chiral catalysts/ligands to obtain enantiomerically pure compounds is a goal synthetic chemists have pursued in recent decades . Chiral Lewis base catalysts have played an important role in asymmetric catalysis .…”

Section: Introductionmentioning

confidence: 99%

Design and Application of Chiral Bifunctional 4-Pyrrolidinopyridines: Powerful Catalysts for Asymmetric Cycloaddition of Allylic N-Ylide

et al. 2022

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We designed bifunctional 4-pyrrolidinopyridines as powerful Lewis base catalysts. The catalyst structure features a 4-hydroxy-2-(hydroxydiphenylmethyl)pyrrolidine-1-formyl group at the pyridine’s C3 site and a chiral side arm at the C2 position of the p-pyrrolidine ring. An operationally simple three-step synthetic route allows for efficient and economical catalyst preparation. In comparison with other Lewis bases, the catalyst exhibits excellent efficiency and stereoselectivity in the asymmetric (3 + 2) cycloaddition of allylic N-ylide generated in situ from a pyrazolone-derived Morita–Baylis–Hillman carbonate, providing a powerful platform for the construction of chiral spiropyrazolone derivatives. The reaction mechanism was thoroughly studied. Control experiments and DFT calculations illustrated the origin of the chemoselectivity and the stereocontrol model. H-bonding is crucial for the control of enantioselectivity and diastereoselectivity. The catalyst was also successfully applied in other reactions, such as an acylative dynamic kinetic resolution to synthesize a chiral phthalidyl ester, including the prodrug Talmetacin.

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Nickel‐Catalyzed Enantioconvergent Allenylic Amination of Allenols Activated by Hydrogen‐Bonding Interaction with Methanol

Zhang,

Lin,

et al. 2024

Angewandte Chemie

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The ubiquitous nature of amines in drug compounds, bioactive molecules and natural products has fueled intense interest in their synthesis. Herein, we introduce a nickel‐catalyzed enantioconvergent allenylic amination of methanol‐activated allenols. This protocol affords a diverse array of functionalized allenylic amines in high yields and with excellent enantioselectivities. The synthetic potential of this method is demonstrated by employing bioactive amines as nucleophiles and conducting gram‐scale reactions. Furthermore, mechanistic investigations and DFT calculations elucidate the role of methanol as an activator in the nickel‐catalyzed reaction, facilitating the oxidative addition of the C–O bond of allenols through hydrogen‐bonding interactions. The remarkable outcomes arise from a rapid racemization of allenols enabled by the nickel catalyst and from highly enantioselective dynamic kinetic asymmetric transformation of η3‐alkadienylnickel intermediates.

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Development of Earth-Abundant Metals-Catalyzed Enantioselective Alkenylations Using Alkenyl Metal Reagents

Cited by 13 publications

References 186 publications

Enantioselective Reductive Conjugate Alkenylation of α,β-Unsaturated Ketones and Amides via Nickel Catalysis

Enantioselective Reductive Conjugate Alkenylation of α,β-Unsaturated Ketones and Amides via Nickel Catalysis

Design and Application of Chiral Bifunctional 4-Pyrrolidinopyridines: Powerful Catalysts for Asymmetric Cycloaddition of Allylic N-Ylide

Nickel‐Catalyzed Enantioconvergent Allenylic Amination of Allenols Activated by Hydrogen‐Bonding Interaction with Methanol

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