Making Full Use of TMSCF₃: Deoxygenative Trifluoromethylation/Silylation of Amides

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 19286 - 19294

Опубликована: Июль 3, 2024

As one of the most powerful trifluoromethylation reagents, (trifluoromethyl)trimethylsilane (TMSCF3) has been widely used for synthesis fluorine-containing molecules. However, to best our knowledge, simultaneous incorporation both TMS- and CF3- groups this reagent onto same carbon products not realized. Herein, we report an unprecedented SmI2/Sm promoted deoxygenative difunctionalization amides with TMSCF3, in which silyl trifluoromethyl are incorporated into final product, yielding α-silyl-α-trifluoromethyl amines high efficiency. Notably, group could be further transformed other functional groups, providing a new method α-quaternary α-CF3-amines.

Язык: Английский

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Merging SOMO activation with transition metal catalysis: Deoxygenative functionalization of amides to β-aryl amines

Science Advances, Год журнала: 2025, Номер 11(3)

Опубликована: Янв. 17, 2025

Singly occupied molecular orbital (SOMO) activation of in situ generated enamines has achieved great success (asymmetric) α-functionalization carbonyl compounds. However, examples on the use this mode transformations other functional groups are rare, and combination SOMO with transition metal catalysis is still less explored. In area deoxygenative functionalization amides, intermediates such as iminium ions were often to result formation α-functionalized amines. contrast, direct deoxygenation amides β-functionalized amines highly appealing yet remains scarcely investigated. Here, a arylation aryl halides was developed via multicatalysis iridium/photoredox/nickel/iridium, affording β-aryl high efficiency. The key reaction enamine synergy Ni-catalyzed arylation, which conjunction two compatible Ir-catalyzed reduction processes.

Язык: Английский

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Deoxygenative photochemical alkylation of secondary amides enables a streamlined synthesis of substituted amines

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 22, 2025

Abstract Secondary amines are vital functional groups in pharmaceuticals, agrochemicals, and natural products, necessitating efficient synthetic methods. Traditional approaches, including N -monoalkylation reductive amination, suffer from limitations such as poor chemoselectivity complexity. Herein, we present a streamlined deoxygenative photochemical alkylation of secondary amides, enabling the synthesis α-branched amines. Our method leverages triflic anhydride-mediated semi-reduction amides to imines, followed by radical step. This approach broadens utility facilitating late-stage modifications drug-like molecules saturated -substituted heterocycles. The pivotal role flow technology developing scalable robust process underscores practicality this method, significantly expanding organic chemist’s toolbox for complex amine synthesis.

Язык: Английский

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Organocatalytic Deoxygenative [3+2] Cycloaddition of N-Hydroxyamides with Alkynes to Access Isoxazoles

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 12, 2024

Although the transition-metal-catalyzed [3+2] cycloadditions to access isoxazoles have been described well, organocatalytic methods remain underdeveloped. Herein, we report use of an organophosphine catalyst for preparation a series with exceptional regioselectivity via cycloaddition

Язык: Английский

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