Enantio‐ and Regioselective NiH‐Catalyzed Reductive Hydroarylation of Vinylarenes with Aryl Iodides

He, Yuli; Liu, Chuang; Yu, Lei; Zhu, Shaolin

doi:10.1002/anie.202010386

Cited by 111 publications

(43 citation statements)

References 89 publications

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“…Based on the mechanistic results and relevant literature reports, [9, 11] a plausible mechanism is depicted in Scheme 3. First, nickel (I) reduced from Ni II precursor [9, 10, 15] undergoes transmetalation with silane with assistance of base to generate nickel (I) hydride intermediate A . According to the results from Equation (3), irreversible enantioselective hydrometalation of acrylamides to give alkyl nickel intermediates B (via path a) or B′ (via path b).…”

Section: Methodsmentioning

confidence: 99%

Regio‐ and Enantioselective Ni‐Catalyzed Formal Hydroalkylation, Hydrobenzylation, and Hydropropargylation of Acrylamides to α‐Tertiary Amides

Shi

Xing

et al. 2020

Angewandte Chemie

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The development of enantioselective alkyl-alkyl cross-couplings with coinstantaneous formation of a stereogenic center without the use of sensitive organometallic species is attractive yet challenging. Herein, we report the intermolecular regio-and enantioselective formal hydrofunctionalizations of acrylamides, forging a stereogenic center a-position to the newly formed C sp3 -C sp3 bond for the first time. The use of a newly developed chiral ligand enables the electronicallyreversed formal hydrofunctionalizations, including hydroalkylation, hydrobenzylation, and hydropropargylation, offering an efficient way to access diverse enantioenriched amides with a tertiary a-stereogenic carbon center which is facile to racemize. This operationally simple protocol allows for the anti-Markovnikov enantioselective hydroalkylation, and unprecedented hydrobenzylation, hydropropargylation under mild conditions with excellent functional group compatibility, delivering a wide range of amides with excellent levels of enantioselectivity.Scheme 1. Alkyl-alkyl cross-coupling strategies to construct stereogenic carbon center.

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Section: Methodsmentioning

confidence: 99%

Regio‐ and Enantioselective Ni‐Catalyzed Formal Hydroalkylation, Hydrobenzylation, and Hydropropargylation of Acrylamides to α‐Tertiary Amides

Shi

Xing

et al. 2020

Angewandte Chemie

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“…Very recently, Zhu and co‐workers employed BiIM ligand 20 in NiH‐catalyzed reductive hydroarylation of aromatic olefins and aryl iodides (Scheme 20). [ 47 ] BiIM ligand 20 played an important role in improving the reaction outcome. In the presence of 20 , the hydroarylation proceeded smoothly under room temperature, yielding the chiral 1,1‐diarylalkanes with moderate to good yields and up to 97% ee .…”

Section: Bidentate Imidazoline Ligandsmentioning

confidence: 99%

Chiral Imidazoline Ligands and Their Applications in Metal‐Catalyzed Asymmetric Synthesis^†

2021

Chin. J. Chem.

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As a structural analog of oxazoline, imidazoline (4,5‐dihydroimidazole) has received much attention in the rational design of chiral ligands. The additional N‐substituent provides broader space for fine‐tuning of electronic and steric effects, and it offers a good handle for immobilizing onto solid supports. In the past decades, imidazoline ring has emerged as a powerful candidate for the design of chiral nitrogen‐containing ligands, as well as a significant alternative for oxazoline ring. Various chiral imidazoline ligands have been designed and utilized in asymmetric organic reactions. These new catalysts can not only be applied in classical reactions, but also be employed to develop new organic reactions with high enantioselectivities. This review provides an overview of chiral imidazoline ligands. Their applications in asymmetric synthesis are also summarized.

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“…Recently, we reported the enantioselective hydroarylation of styrenes using a novel chiral nickel-bis(imidazoline) catalyst (Fig. 1c , i) 40 . In this process, an asymmetric center was generated and controlled at the carbon derived from the olefin.…”

Section: Introductionmentioning

confidence: 99%

NiH-catalyzed asymmetric hydroarylation of N-acyl enamines to chiral benzylamines

et al. 2021

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Enantiomerically pure chiral amines and related amide derivatives are privilege motifs in many pharmacologically active molecules. In comparison to the well-established hydroamination, the transition metal-catalysed asymmetric hydrofunctionalization of enamines provides a complementary approach for their construction. Here we report a NiH-catalysed enantio- and regioselective reductive hydroarylation of N-acyl enamines, allowing for the practical access to a broad range of structurally diverse, enantioenriched benzylamines under mild, operationally simple reaction conditions.

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Enantio‐ and Regioselective NiH‐Catalyzed Reductive Hydroarylation of Vinylarenes with Aryl Iodides

Cited by 111 publications

References 89 publications

Regio‐ and Enantioselective Ni‐Catalyzed Formal Hydroalkylation, Hydrobenzylation, and Hydropropargylation of Acrylamides to α‐Tertiary Amides

Regio‐ and Enantioselective Ni‐Catalyzed Formal Hydroalkylation, Hydrobenzylation, and Hydropropargylation of Acrylamides to α‐Tertiary Amides

Chiral Imidazoline Ligands and Their Applications in Metal‐Catalyzed Asymmetric Synthesis^†

NiH-catalyzed asymmetric hydroarylation of N-acyl enamines to chiral benzylamines

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Enantio‐ and Regioselective NiH‐Catalyzed Reductive Hydroarylation of Vinylarenes with Aryl Iodides

Cited by 111 publications

References 89 publications

Regio‐ and Enantioselective Ni‐Catalyzed Formal Hydroalkylation, Hydrobenzylation, and Hydropropargylation of Acrylamides to α‐Tertiary Amides

Regio‐ and Enantioselective Ni‐Catalyzed Formal Hydroalkylation, Hydrobenzylation, and Hydropropargylation of Acrylamides to α‐Tertiary Amides

Chiral Imidazoline Ligands and Their Applications in Metal‐Catalyzed Asymmetric Synthesis†

NiH-catalyzed asymmetric hydroarylation of N-acyl enamines to chiral benzylamines

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Product

Resources

About

Chiral Imidazoline Ligands and Their Applications in Metal‐Catalyzed Asymmetric Synthesis^†