Iridium-catalyzed reductive γ-lactonization of <i>ortho</i>-acylbenzoic acids in water: sustainable access to phthalides

Chen, Yang; Zhang, Jingyu; Du, Hongguang; Luo, Renshi; Xu, Jiaxi; Yang, Zhanhui

doi:10.1039/d3qo02019c

Org. Chem. Front.

2024

DOI: 10.1039/d3qo02019c

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Iridium-catalyzed reductive γ-lactonization of ortho-acylbenzoic acids in water: sustainable access to phthalides

Yang Chen,

Jingyu Zhang,

Hongguang Du

et al.

Abstract: Iridium-catalyzed reductive γ-lactonization of ortho-acylbenzoic acids in water provides a practical and sustainable route to phthalides.

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Cited by 4 publications

References 89 publications

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Copper‐Catalyzed Asymmetric Hydrogenation of Unsymmetrical ortho‐Br Substituted Benzophenones

Guan,

Luo,

Wang

et al. 2024

Angewandte Chemie

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The asymmetric hydrogenation of benzophenones, catalyzed by low‐activity earth‐abundant metal copper, has hitherto remained a challenge due to the substrates equipped with two indistinguishably similar aryl groups. In this study, we demonstrated that the prochiral carbon of the ortho‐bromine substrate exhibits the highest electrophilicity and high reactivity among the ortho‐halogen substituted benzophenones, as determined by the Fukui function (f+) analysis and hydrogenation reaction. Considering that the enantiodirecting functional bromine group can be easily derivatized and removed in the products, we successfully achieved a green copper‐catalyzed asymmetric hydrogenation of ortho‐bromine substituted benzophenones. This method yielded a series of chiral benzhydrols with excellent results. The utility of this protocol has been validated through a gram‐scale reaction and subsequent product transformations. Independent gradient model based on Hirshfeld partition (IGMH) and energy decomposition analysis (EDA) indicate that the CH⋅⋅⋅HC multiple attractive dispersion interactions (MADI) effect between the catalyst and substrate enhances the catalyst's activity.

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Copper‐Catalyzed Asymmetric Hydrogenation of Unsymmetrical ortho‐Br Substituted Benzophenones

Guan,

Luo,

Wang

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

show abstract

Copper‐Catalyzed Asymmetric Hydrogenation of Unsymmetrical ortho‐Br Substituted Benzophenones

Guan,

Luo,

Wang

et al. 2024

Angew Chem Int Ed

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En Route to Diastereopure Polycyclic γ‐Lactones by Iridium‐Catalyzed Hydride Transfer^†

Chen,

Zhang,

Wang

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryThe reductive lactonization strategy provides an efficient access to diastereoenriched polycyclic γ‐lactones. However, it is still a formidable challenge to develop an efficient and versatile protocol with excellent levels of diastereocontrol. Herein, we provide a highly diastereoselective and efficient route to diastereopure bi‐ and polycyclic γ‐lactones, by means of an iridium‐catalyzed hydride transfer strategy. This method features high levels of diastereocontrol, broad substrate scope, and high catalyst efficiency (S/C = up to 5000). Mechanistic studies suggest that the iridium hydride formation might be the rate‐determining step, and that the hydride transfer step be the diastereo‐determining step. The large steric hindrance of the iridium hydride species and intramolecular hydrogen bonding are critically key to the diastereocontrol of the hydride transfer process. From the perspectives of configurational analysis and Duniz angles of attack, the nature of diastereocontrol is well rationalized. A more general empirical rule based on facial selectivity analysis for explaining and predicting the stereochemistry is also proposed.

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Iridium-catalyzed reductive γ-lactonization of ortho-acylbenzoic acids in water: sustainable access to phthalides

Abstract: Iridium-catalyzed reductive γ-lactonization of ortho-acylbenzoic acids in water provides a practical and sustainable route to phthalides.

Cited by 4 publications

References 89 publications

Copper‐Catalyzed Asymmetric Hydrogenation of Unsymmetrical ortho‐Br Substituted Benzophenones

Copper‐Catalyzed Asymmetric Hydrogenation of Unsymmetrical ortho‐Br Substituted Benzophenones

Copper‐Catalyzed Asymmetric Hydrogenation of Unsymmetrical ortho‐Br Substituted Benzophenones

En Route to Diastereopure Polycyclic γ‐Lactones by Iridium‐Catalyzed Hydride Transfer^†

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Iridium-catalyzed reductive γ-lactonization of ortho-acylbenzoic acids in water: sustainable access to phthalides

Abstract: Iridium-catalyzed reductive γ-lactonization of ortho-acylbenzoic acids in water provides a practical and sustainable route to phthalides.

Cited by 4 publications

References 89 publications

Copper‐Catalyzed Asymmetric Hydrogenation of Unsymmetrical ortho‐Br Substituted Benzophenones

Copper‐Catalyzed Asymmetric Hydrogenation of Unsymmetrical ortho‐Br Substituted Benzophenones

Copper‐Catalyzed Asymmetric Hydrogenation of Unsymmetrical ortho‐Br Substituted Benzophenones

En Route to Diastereopure Polycyclic γ‐Lactones by Iridium‐Catalyzed Hydride Transfer†

Contact Info

Product

Resources

About

En Route to Diastereopure Polycyclic γ‐Lactones by Iridium‐Catalyzed Hydride Transfer^†