Allylation of C‐, N‐, and O‐Nucleophiles via a Mechanochemically‐Driven Tsuji–Trost Reaction Suitable for Late‐Stage Modification of Bioactive Molecules

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(1)

Опубликована: Ноя. 6, 2023

Abstract We present the first solvent‐free, mechanochemical protocol for a palladium‐catalyzed Tsuji–Trost allylation. This approach features exceptionally low catalyst loadings (0.5 mol %), short reaction times (<90 min), and simple setup, eliminating need air or moisture precautions, making process highly efficient environmentally benign. introduce solid, nontoxic, easy‐to‐handle allyl trimethylammonium salts as valuable alternative to volatile hazardous reagents. Our enables allylation of various O ‐, N C ‐nucleophiles in yields up 99 % even structurally complex bioactive compounds, owing its mild conditions exceptional functional group tolerance.

Язык: Английский

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Disentangling the Effect of Pressure and Mixing on a Mechanochemical Bromination Reaction by Solid‐State NMR Spectroscopy**

Chemistry - A European Journal, Год журнала: 2022, Номер 29(12)

Опубликована: Ноя. 29, 2022

Mechanical forces, including compressive stresses, have a significant impact on chemical reactions. Besides the preparative opportunities, mechanochemical conditions benefit from absence of any organic solvent, possibility synthetic acceleration and unique reaction pathways. Together with an accurate characterization ball-milling products, development deeper mechanistic understanding occurring transformations at molecular level is critical for fully grasping potential mechanosynthesis. We herein studied bromination cyclic sulfoximine in mixer mill used solid-state nuclear magnetic resonance (NMR) spectroscopy structural products. Magic-angle spinning (MAS) was applied elucidating product mixtures taken milling jar without introducing further post-processing sample. Ex situ 13 C-detected NMR spectra products showed formation crystalline solid phase regioselective S-aryl group heterocycle position 4. Completion reached less than 30 minutes as deduced spectra. The can also be achieved by stirring, but then, longer time required. Mixing educts rotor allows to get insights into enables detection intermediate. pressure alone induced MAS not sufficient lead full conversion occurs slower scales ball mill, which crucial analysing NMR. Our data suggest that top centrifugal efficient mixing starting materials required reaching complete reaction.

Язык: Английский

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Nickel‐Catalyzed Intramolecular Alkene Difunctionalization by Ball‐Milling

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(9), С. 1477 - 1484

Опубликована: Апрель 14, 2023

Abstract A mechanochemical nickel‐catalyzed intramolecular difunctionalization reaction of alkene tethered aryl halides with alkyl is herein described. This method allows for synthesis 3,3‐disubstituted heterocycles, namely oxindoles, shorter times than solution‐phase counterparts. Additionally, this process solvent minimized, DMA used in liquid‐assisted grinding (LAG) quantities and circumvents the need chemical activation terminal reductant (manganese) through mechanical grinding. The can be scaled up to yield over a gram product modest enantioinduction possible by utilizing chiral PyrOx ligand. magnified image

Язык: Английский

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Mechanochemical Iron‐Catalyzed Nitrene Transfer Reactions: Direct Synthesis of N‐Acyl Sulfonimidamides from Sulfinamides and Dioxazolones

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(5)

Опубликована: Дек. 7, 2023

A mechanochemical synthesis of sulfonimidamides by iron(II)-catalyzed exogenous ligand-free N-acyl nitrene transfer to sulfinamides is reported. The one-step method tolerates a wide range with various substituents under solvent-free ambient conditions. Compared its solution-phase counterpart, this approach shows better conversion and chemoselectivity. Mechanistic investigations ESI-MS revealed the generation crucial iron intermediates.

Язык: Английский

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Rhodium(II)-Catalyzed N–H Insertions of Carbenes under Mechanochemical Conditions

Organic Letters, Год журнала: 2024, Номер 26(7), С. 1511 - 1516

Опубликована: Фев. 15, 2024

Under mechanochemical conditions in a mixer mill, Rh

Язык: Английский

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