Phen-2NO, a new <i>C</i><sub>2</sub>-symmetric rigid-featured tetradentate ligand, and its application in the asymmetric alkylation reaction of indoles

Chen, Zi-Yue; Xu, Ke-Lan; Wang, Xi-Rui; Hu, Pan; Jiang, Wei-Yan; Dai, Yi-Feng; Peng, Li-Jun; Liu, Xiong-Li

doi:10.1039/d4nj00088a

New J. Chem.

2024

DOI: 10.1039/d4nj00088a

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Phen-2NO, a new C₂-symmetric rigid-featured tetradentate ligand, and its application in the asymmetric alkylation reaction of indoles

Zi-Yue Chen,

Ke-Lan Xu,

Xi-Rui Wang

et al.

Abstract: As phenanthroline (phen) possesses great coordination ability with various ions, the development of new chiral phen ligands is in great demand in asymmetric catalysis. Herein, we rationally designed and developed...

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2024

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Cited by 3 publications

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Modular Chiral Bithiophene‐2NO Ligands: Synthesis and Application in Asymmetric Palladium(II)‐Catalysed Friedel‐Crafts Alkylation

Zhu,

Li,

Liu

et al. 2024

Adv Synth Catal

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The development of privileged thiophene‐type ligand remains highly desirable, owing to the high coordination ability of sulfur atom to most of the soft metals. Herein, a new class of C2‐symmetric rigid chiral tertiary amine‐derived dioxide ligands with a coordinating bithiophene bridge was developed in a convenient synthetic route with 25‐62% overall yields. The bithiophene‐2NO‐palladium(II) catalyst system was generated in situ and found to be highly capable catalyst in the asymmetric Friedel‐Crafts alkylation of indoles. Excellent yields (up to 92%) and high enantioselectivities (up to >99% ee) are obtained for a wide range of substrates under mild conditions. Control experiments and DFT calculations revealed the origins of the enantioselectivity. This represented the first example of chiral thiophene ligands coordinating with soft metal Pd(II) in the asymmetric Friedel‐Crafts alkylation. Experiments revealed that the counteranion is involved in the stereoselectivity‐determining step in this soft palladium(II) catalysis, and the additional NO and thiophene in ligands can act as the second chelation site and thus reduce the amount of free metal ions for suppressing background reaction in the catalytic system.

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Modular Chiral Bithiophene‐2NO Ligands: Synthesis and Application in Asymmetric Palladium(II)‐Catalysed Friedel‐Crafts Alkylation

Zhu,

Li,

Liu

et al. 2024

Adv Synth Catal

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Modular Synthesis of C₂‐Symmetric Chiral TPy‐BPI Pincer Ligands and Application in Asymmetric Ni(II)‐Catalysed Friedel‐Crafts Alkylation

Cen,

Ding,

Liu

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryTerpyridine ligands have been applied as a class of unique ligands due to their rich coordination chemistry in the catalysis. Herein, we developed a new class of C2‐symmetric chiral terpyridine‐pyrroloimidazolone ligands (TPy‐BPI). Their catalytic activity was evaluated in the asymmetric Friedel‐Crafts alkylation of indoles with 2,3‐dioxopyrrolidines. Excellent yields (up to 92%) and high enantioselectivities (up to 97% ee) are obtained for a wide range of substrates under mild conditions. In addition to 2,3‐dioxopyrrolidines, β,γ‐unsaturated α‐ketoesters were also compatible in the Ni(OTf)2‐TPy‐BPI ligand L1‐catalyzed reaction. Control experiments, single crystal structure of two TPy‐BPI L1‐Ni(OTf)2 complexes, and DFT calculations revealed the origins of the enantioselectivity. To the best of our knowledge, our work is the first report showing that the terpyridine framework contained only two nitrogen atoms coordinating with the metal, and the additional pyridine unit only acted as stereodirecting element, which is different from the previously reported terpyridine ligands containing all three nitrogen atoms coordinating with the metal.

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Axially Chiral Phenanthroline Ligand-Enabled Copper-Catalyzed Enantioselective Arylation of Azonaphthalenes with Arylboronic Acids

Cen,

Zhang,

Wang

2024

Synlett

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Phen-2NO, a new C₂-symmetric rigid-featured tetradentate ligand, and its application in the asymmetric alkylation reaction of indoles

Abstract: As phenanthroline (phen) possesses great coordination ability with various ions, the development of new chiral phen ligands is in great demand in asymmetric catalysis. Herein, we rationally designed and developed...

Cited by 3 publications

References 80 publications

Modular Chiral Bithiophene‐2NO Ligands: Synthesis and Application in Asymmetric Palladium(II)‐Catalysed Friedel‐Crafts Alkylation

Modular Chiral Bithiophene‐2NO Ligands: Synthesis and Application in Asymmetric Palladium(II)‐Catalysed Friedel‐Crafts Alkylation

Modular Synthesis of C₂‐Symmetric Chiral TPy‐BPI Pincer Ligands and Application in Asymmetric Ni(II)‐Catalysed Friedel‐Crafts Alkylation

Axially Chiral Phenanthroline Ligand-Enabled Copper-Catalyzed Enantioselective Arylation of Azonaphthalenes with Arylboronic Acids

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Phen-2NO, a new C2-symmetric rigid-featured tetradentate ligand, and its application in the asymmetric alkylation reaction of indoles

Abstract: As phenanthroline (phen) possesses great coordination ability with various ions, the development of new chiral phen ligands is in great demand in asymmetric catalysis. Herein, we rationally designed and developed...

Cited by 3 publications

References 80 publications

Modular Chiral Bithiophene‐2NO Ligands: Synthesis and Application in Asymmetric Palladium(II)‐Catalysed Friedel‐Crafts Alkylation

Modular Chiral Bithiophene‐2NO Ligands: Synthesis and Application in Asymmetric Palladium(II)‐Catalysed Friedel‐Crafts Alkylation

Modular Synthesis of C2‐Symmetric Chiral TPy‐BPI Pincer Ligands and Application in Asymmetric Ni(II)‐Catalysed Friedel‐Crafts Alkylation

Axially Chiral Phenanthroline Ligand-Enabled Copper-Catalyzed Enantioselective Arylation of Azonaphthalenes with Arylboronic Acids

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Product

Resources

About

Phen-2NO, a new C₂-symmetric rigid-featured tetradentate ligand, and its application in the asymmetric alkylation reaction of indoles

Modular Synthesis of C₂‐Symmetric Chiral TPy‐BPI Pincer Ligands and Application in Asymmetric Ni(II)‐Catalysed Friedel‐Crafts Alkylation