Fast and scalable solvent-free access to Lappert's heavier tetrylenes E{N(SiMe₃)₂}₂ (E = Ge, Sn, Pb) and ECl{N(SiMe₃)₂} (E = Ge, Sn)

Chemical Science, Год журнала: 2023, Номер 14(44), С. 12477 - 12483

Опубликована: Янв. 1, 2023

Iconic Lappert's heavier tetrylenes E{N(SiMe3)2}2 (E = Ge (1), Sn (2), Pb (3)) have been efficiently prepared from GeCl2·(1,4-dioxane), SnCl2 or PbCl2 and Li{N(SiMe3)2} via a completely solvent-free one-pot mechanochemical route followed by sublimation. This fast, high-yielding scalable approach (2 has in 100 mmol scale), which involves small environmental footprint, represents remarkable improvement over any synthetic reported the last five decades, being so far rare example of use mechanochemistry realm main group chemistry. solventless successfully extended to preparation other tetrylenes, such as ECl{N(SiMe3)2} (4), (5)).

Язык: Английский

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Mechanochemical activation of metallic lithium for the generation and application of organolithium compounds in air

Nature Synthesis, Год журнала: 2025, Номер unknown

Опубликована: Фев. 21, 2025

Язык: Английский

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In Situ Generation of Magnesium‐ and Calcium‐Based Grignard Reagents for Amide Synthesis

Chemistry - A European Journal, Год журнала: 2023, Номер 29(40)

Опубликована: Май 16, 2023

The alkaline-earth metals Mg and Ca are too inert for the direct metalation of primary secondary amines. Consequently, activation prior to use is required. Alternatively, Grignard reagents RMgX (R=alkyl, aryl, X=halide) can be applied in However, such a straightforward procedure synthesis alkylcalcium disadvantageous due diverse side reactions, including Wurtz-type C-C coupling ether degradation reactions. Therefore, suspensions magnesium or calcium with amine treated smooth reaction ethyl bromide an ethereal solvent at room temperature. Intermediately formed RAeX (Ae=alkaline-earth metal, i. e., Mg, Ca) either metalates amines yielding corresponding amides situ method (iGMM) adds across C=N bonds imines addition (iGAM). R'2 N-AeX (Ae=Mg: Hauser bases) undergo Schlenk-type ligand exchange reactions homoleptic Ae(NR'2 )2 potentially sparingly soluble AeX2 .

Язык: Английский

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Mechanochemical C−H Arylation and Alkylation of Indoles Using 3 d Transition Metal and Zero‐Valent Magnesium

Chemistry - A European Journal, Год журнала: 2024, Номер 30(26)

Опубликована: Янв. 31, 2024

Although the 3 d transition-metal catalyzed C-H functionalization have been extensively employed to promote formation of valuable carbon-carbon bonds, persistent problems, including use sensitive Grignard reagents and rigorous operations (solvent-drying, inert gas protection, metal pre-activation RMgX addition rate control), still leave great room for further development sustainable methodologies. Herein, we report a mechanochemical technology toward in-situ preparation highly organomagnesium reagents, thus building two general catalytic platforms that enables regioselective arylation alkylation indoles with wide variety halides (including those containing post transformable functionalities heteroaromatic rings). This strategy also brings unique reactivity high step-economy in producing functionalized N-free indole products.

Язык: Английский

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Direct Synthesis of Organothianthrenium Salts under Ball Milling Conditions

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер 23(19), С. 4636 - 4640

Опубликована: Янв. 1, 2025

The solvent-free mechanochemical method enables efficient synthesis of diverse organothianthrenium salts via ball-milling technique, eliminating the need for hazardous reactants, inert atmosphere, and complex reaction setups.

Язык: Английский

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