Asymmetric transfer hydrogenation of fluorinated ketone and imine derivatives: An efficient access to valuable building blocks

Bacheley, Lucas; Guillamot, Gérard; Phansavath, Phannarath; Ratovelomanana-Vidal, Virginie

doi:10.1016/j.tet.2023.133781

Tetrahedron

2024

DOI: 10.1016/j.tet.2023.133781

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Asymmetric transfer hydrogenation of fluorinated ketone and imine derivatives: An efficient access to valuable building blocks

Lucas Bacheley,

Gérard Guillamot,

Phannarath Phansavath

et al.

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2024

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Cited by 3 publications

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Iridium‐Catalyzed Asymmetric Transfer Hydrogenation for Facile Access to Optically Active Dihydrodibenzo‐Fused Azepines

He,

Yang,

et al. 2024

Adv Synth Catal

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The asymmetric transfer hydrogenation of various dibenzo‐fused azepines including 5H‐dibenzo[b,e][1,4]diazepines, dibenzo[b,f][1,4]thiazepines and 11H‐dibenzo[b,e]azepines using chiral iridium diamine catalysts and HCO2H/NEt3 as the hydrogen source has been accomplished. A rang of chiral 10,11‐dihydro‐5H‐dibenzo[b,e][1,4]diazepines, 10,11‐dihydrodibenzo[b,f][1,4]thiazepine and 6,11‐dihydro‐5H‐dibenzo[b,e]azepines have been prepared in 82‐94% yields with 82‐99% ee. Diversely substituted substrates are suitable for this transformation, and a number of functional groups are tolerated. The enantiocontrol is achieved via judicious choice of catalyst, additive and hydrogen source. The synthetic potential of this reaction is explored through gram‐scale reactions without loss of reactivity and optical purity and further transformations on products.

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Iridium‐Catalyzed Asymmetric Transfer Hydrogenation for Facile Access to Optically Active Dihydrodibenzo‐Fused Azepines

He,

Yang,

et al. 2024

Adv Synth Catal

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Asymmetric Transfer Hydrogenation of 3‐Substituted 2H‐1,4‐Benzoxazines under Tethered Cp*Rh(III)‐Diamine Catalysis with Unexpected Reversal of Enantioselectivity

Li,

Yang,

et al. 2024

Adv Synth Catal

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The asymmetric transfer hydrogenation of 3‐substituted 2H‐1,4‐benzoxazines with an azeotropic mixture of HCO2H/NEt3 (5/2) using tethered Cp*Rh(III)‐diamine catalysis has been realized. This process allows access to a broad range of chiral 3,4‐dihydro‐2H‐1,4‐benzoxazines in high yields with up to 99% ee, and tolerates a variety of functional groups. The enantiocontrol is achieved by the judicious choice of catalyst and hydrogen source. This reaction proceeds with unexpected reversal of enantioselectivity, which is attributed to the acidic reaction conditions and the hydrogen bond between the N−H of the rhodium species and the O atom in the substrate.

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Catalytic Asymmetric Transfer Hydrogenation of β,γ-Unsaturated α-Diketones

Zhao,

Dong,

Liu

et al. 2024

J. Am. Chem. Soc.

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Asymmetric transfer hydrogenation (ATH) has been recognized as a highly valuable strategy that allows access to enantioenriched substances and has been widely applied in the industrial production of drug molecules. However, despite the great success in ATH of ketones, highly efficient, regio-and stereoselective ATH on enones remains underdeveloped. Moreover, optically pure acyloins and 1,2-diols are both extremely useful building blocks in organic synthesis, medicinal chemistry, and materials science, but concise asymmetric approaches allowing access to different types of acyloins and 1,2-diols have scarcely been discovered. We report in this paper the first highly efficient ATH of readily accessible β,γ-unsaturated α-diketones. The protocol affords four types of enantioenriched acyloins and four types of optically pure 1,2-diols in highly regio-and stereoselective fashion. The synthetic value of this work has been showcased by the divergent synthesis of four related natural products. Moreover, systematic mechanistic studies and density functional theory (DFT) calculations have illustrated the origin of the reactivity divergence, revealed the different roles of aromatic and aliphatic substituents in the substrates, and provided a range of unique mechanistic rationales that have not been disclosed in ATH-related studies.

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Asymmetric transfer hydrogenation of fluorinated ketone and imine derivatives: An efficient access to valuable building blocks

Cited by 3 publications

References 74 publications

Iridium‐Catalyzed Asymmetric Transfer Hydrogenation for Facile Access to Optically Active Dihydrodibenzo‐Fused Azepines

Iridium‐Catalyzed Asymmetric Transfer Hydrogenation for Facile Access to Optically Active Dihydrodibenzo‐Fused Azepines

Asymmetric Transfer Hydrogenation of 3‐Substituted 2H‐1,4‐Benzoxazines under Tethered Cp*Rh(III)‐Diamine Catalysis with Unexpected Reversal of Enantioselectivity

Catalytic Asymmetric Transfer Hydrogenation of β,γ-Unsaturated α-Diketones

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