Biocatalytic Construction of Chiral Pyrrolidines and Indolines via Intramolecular C(sp<sup>3</sup>)–H Amination

Qin, Zi-Yang; Gao, Shilong; Zou, Yike; Liu, Zhen; Wang, James B.; Houk, Kendall N.; Arnold, Frances H.

doi:10.1021/acscentsci.3c00516

ACS Cent. Sci.

2023

DOI: 10.1021/acscentsci.3c00516

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Biocatalytic Construction of Chiral Pyrrolidines and Indolines via Intramolecular C(sp³)–H Amination

Zi-Yang Qin,

Shilong Gao,

Yike Zou

et al.

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2024

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Cited by 12 publications

References 45 publications

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Iron Corrole‐Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [Fe^V(Cor)(NAd)]

You,

Shing,

et al. 2024

Advanced Science

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As nitrogen analogues of iron‐oxo species, high‐valent iron‐imido species have attracted great interest in the past decades. FeV‐alkylimido species are generally considered to be key reaction intermediates in Fe(III)‐catalyzed C(sp3)─H bond aminations of alkyl azides but remain underexplored. Here, it is reported that iron‐corrole (Cor) complexes can catalyze a wide range of intramolecular C─H amination reactions of alkyl azides to afford a variety of 5‐, 6‐ and 7‐membered N‐heterocycles, including alkaloids and natural product derivatives, with up to 3880 turnover numbers (TONs) and excellent diastereoselectivity (>99:1 d.r.). Mechanistic studies including density functional theory (DFT) calculations and intermolecular hydrogen atom abstraction (HAA) reactions reveal key reactive FeV‐alkylimido intermediates. The [FeV(Cor)(NAd)] (Ad = adamantyl) complex is independently prepared and characterized through electron paramagnetic resonance (EPR), resonance Raman (rR) measurement, and X‐ray photoelectron spectroscopy (XPS). This complex is reactive toward HAA reactions with kinetic isotope effects (KIEs) similar to [Fe(Cor)]‐catalyzed intramolecular C─H amination of alkyl azides.

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Iron Corrole‐Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [Fe^V(Cor)(NAd)]

You,

Shing,

et al. 2024

Advanced Science

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Intermolecular Enantioselective Amination Reactions Mediated by Visible Light and a Chiral Iron Porphyrin Complex

Ahmed,

Ghosh,

Breitenlechner

et al. 2024

Angewandte Chemie

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In the presence of 1 mol% of a chiral iron porphyrin catalyst, various 3‐arylmethyl‐substituted 2‐quinolones and 2‐pyridones underwent an enantioselective amination reaction (20 examples; 93‐99% ee). The substrates were used as the limiting reagents, and fluorinated aryl azides (1.5 equiv.) served as nitrene precursors. The reaction is triggered by visible light which allows a facile dediazotation at ambient temperature. The selectivity of the reaction is governed by a two‐point hydrogen bond interaction between the ligand of the iron catalyst and the substrate. Hydrogen bonding directs the amination to a specific hydrogen atom within the substrate that is displaced by the nitrogen substituent either in a concerted fashion or by a rebound mechanism.

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Intermolecular Enantioselective Amination Reactions Mediated by Visible Light and a Chiral Iron Porphyrin Complex

Ahmed,

Ghosh,

Breitenlechner

et al. 2024

Angew Chem Int Ed

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Biocatalytic Construction of Chiral Pyrrolidines and Indolines via Intramolecular C(sp³)–H Amination

Cited by 12 publications

References 45 publications

Iron Corrole‐Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [Fe^V(Cor)(NAd)]

Iron Corrole‐Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [Fe^V(Cor)(NAd)]

Intermolecular Enantioselective Amination Reactions Mediated by Visible Light and a Chiral Iron Porphyrin Complex

Intermolecular Enantioselective Amination Reactions Mediated by Visible Light and a Chiral Iron Porphyrin Complex

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Biocatalytic Construction of Chiral Pyrrolidines and Indolines via Intramolecular C(sp3)–H Amination

Cited by 12 publications

References 45 publications

Iron Corrole‐Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [FeV(Cor)(NAd)]

Iron Corrole‐Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [FeV(Cor)(NAd)]

Intermolecular Enantioselective Amination Reactions Mediated by Visible Light and a Chiral Iron Porphyrin Complex

Intermolecular Enantioselective Amination Reactions Mediated by Visible Light and a Chiral Iron Porphyrin Complex

Contact Info

Product

Resources

About

Biocatalytic Construction of Chiral Pyrrolidines and Indolines via Intramolecular C(sp³)–H Amination

Iron Corrole‐Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [Fe^V(Cor)(NAd)]

Iron Corrole‐Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [Fe^V(Cor)(NAd)]