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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Photo‐induced Desulfurative Processes for Carbon Radical Generation

ChemCatChem, Год журнала: 2023, Номер 15(20)

Опубликована: Июль 25, 2023

Abstract Thiols constitute an important family among sulfur‐containing compounds, with well‐established applications in various fields ranging from medicine to material science. For instance, thiol residues are good hydrogen donors which reduce radical species biological or chemical processes. However, even though the S−H bond activation of thiols for providing access thiyl radicals has been largely studied, desulfurative processes affording carbon‐based by C−S have less explored. In recent years, photoredox catalysis become prevalent method generation under soft reaction conditions readily available starting materials visible light. this context, studies devoted development photocatalytic procedures aiming at desulfurization derivatives leading new C−H, C−C C‐Het formation reactions. This review will cover synthetic methodologies and strategies photo‐mediated native thiols, thioethers, sulfonium salts xanthates organic compounds. emerging field is especially interesting transformations cysteine peptide derivatives.

Язык: Английский

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Asymmetric Deoxygenative Functionalization of Secondary Amides with Vinylpyridines Enabled by a Triple Iridium-Photoredox-Chiral Phosphoric Acid System

Organic Letters, Год журнала: 2024, Номер 26(12), С. 2483 - 2488

Опубликована: Март 15, 2024

An enantioselective deoxygenative functionalization of secondary amides with vinylpridines is developed by merging relay iridium catalysis and cooperative photoredox-chiral Brønsted acid catalysis, affording a series valuable chiral amines in moderate to good yields enantioselectivities. The intriguing multiple catalytic system invoking triple-catalysis was found be the key success current reactions, which may stimulate further development methodologies for asymmetric transformations amides.

Язык: Английский

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Deoxygenative alkylation of tertiary amides using alkyl iodides under visible light

Science China Chemistry, Год журнала: 2022, Номер 65(11), С. 2231 - 2237

Опубликована: Июль 18, 2022

Язык: Английский

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Synthesis of (–)-Sedacryptine and (–)-Geissman-Waiss Lactone by Applying Methods for the Direct Transformation of Amides

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(3), С. 988 - 988

Опубликована: Янв. 1, 2025

Язык: Английский

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α-Aminocarbene-Mediated Si–H Insertion: Deoxygenative Silylation of Aromatic Amides with Silanes

The Journal of Organic Chemistry, Год журнала: 2022, Номер 88(1), С. 594 - 601

Опубликована: Дек. 15, 2022

While metal carbene-mediated Si–H insertion reactions have become a powerful strategy to build new C–Si bonds, the utilization of α-aminocarbene intermediates generated from readily available precursors in reaction remains longstanding challenge. Herein, we develop practical and general synthesize α-aminosilanes through deoxygenative cross-coupling amides silanes mediated by Sm/SmI2. Given simplicity versatility, this methodology represents fascinating example for effective inert as organic synthesis.

Язык: Английский

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Deoxygenative Radical Boration of Inert Amides via a Combination of Relay and Cooperative Catalysis

Chemistry - A European Journal, Год журнала: 2023, Номер 29(35)

Опубликована: Апрель 19, 2023

One of the most challenging tasks in organic synthesis is to develop novel methodologies for rapid construction complex molecules starting from easily available yet inert raw materials. In this context, multi-catalysis strategies have attracted great attention discovery new reactivity profiles that may allow access many difficult or unattainable transformations. So far deoxygenative functionalization ubiquitous amides usually achieved by nucleophilic attack on imine iminium ion intermediate formed via activation C=O bond, and these reagents were often confined C-based nucleophiles, which largely limited diversity resultant amines. Herein, we disclose a combined strategy relay cooperative catalysis with triple iridium-photoredox-organocatalysis system achieve an unprecedented reductive boration amides, affording valuable α-amino boron products are viable building blocks. transformation, Ir-catalyzed semi-reduction successfully incorporated photo-organic catalyzed boryl radical addition, thus delivering corresponding α-boryl amines high efficiency.

Язык: Английский

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Deoxygenative arylation of secondary amides by merging iridium catalysis with electrochemical radical cross-coupling

Green Chemistry, Год журнала: 2023, Номер 25(22), С. 9080 - 9085

Опубликована: Янв. 1, 2023

A deoxygenative arylation of amides using aromatic nitriles via merging Ir-catalyzed amide reduction with electrochemistry has been achieved, which may provide an alternative strategy for access to value-added amines from inert amides.

Язык: Английский

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Iridium‐Catalyzed Reductive (3+2) Annulation of Lactams Enabling the Rapid Total Synthesis of (±)‐Eburnamonine

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(6)

Опубликована: Дек. 13, 2023

A reductive (3+2) annulation of lactams through iridium-catalyzed hydrosilylation and photoredox coupling with α-bromoacetic acid was developed. The the lactam carbonyl group subsequent elimination provide a transient cyclic enamine, which undergoes in one-pot process. developed conditions show high functional-group tolerance N,O-acetals containing quaternary carbon center. resulting undergo variety acid-mediated nucleophilic addition reactions via iminium ions to give substituted amines. sequence including successfully applied four-step total synthesis (±)-eburnamonine.

Язык: Английский

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