Advances in Mechanochemical C─H Functionalization: A Comparative Study with Solvent‐Based Approaches DOI Creative Commons
N. Narayanan, Michael Schnürch

ChemCatChem, Год журнала: 2025, Номер unknown

Опубликована: Май 31, 2025

Abstract This review provides an overview on recent progress in mechanochemical transition metal catalyzed C─H functionalization. Solventless operation and enhanced reaction efficiency makes synthesis a more sustainable alternative to conventional approaches. By including comparison between methods solvent‐based protocols, this chemists with valuable insights into the relative sustainability of these solventless strategies. enables informed decision‐making when selecting for functionalization based specific needs. Moreover, identifies existing gaps discusses necessary steps establish it as mainstream approach. bridging gaps, can further enhance utility adoption methodologies, contributing practices synthetic chemistry.

Язык: Английский

Recent Advances in Alkenyl sp2 C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications DOI
Mingzhu Lu, Jeffrey Goh, Manikantha Maraswami

и другие.

Chemical Reviews, Год журнала: 2022, Номер 122(24), С. 17479 - 17646

Опубликована: Окт. 14, 2022

Alkenes and their derivatives are featured widely in a variety of natural products, pharmaceuticals, advanced materials. Significant efforts have been made toward the development new practical methods to access this important class compounds by selectively activating alkenyl C(sp2)–H bonds recent years. In comprehensive review, we describe state-of-the-art strategies for direct functionalization sp2 C–H C–F until June 2022. Moreover, metal-free, photoredox, electrochemical also covered. For clarity, review has divided into two parts; first part focuses on currently available using different alkene as starting materials, second describes bond easily accessible gem-difluoroalkenes material. This includes scope, limitations, mechanistic studies, stereoselective control (using directing groups well metal-migration strategies), applications complex molecule synthesis where appropriate. Overall, aims document considerable advancements, current status, emerging work critically summarizing contributions researchers working fascinating area is expected stimulate novel, innovative, broadly applicable functionalizations coming

Язык: Английский

Процитировано

155

Mechanochemical Synthesis of Aryl Fluorides by Using Ball Milling and a Piezoelectric Material as the Redox Catalyst DOI
Xiaohong Wang, Xuemei Zhang, Xue Li

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(39)

Опубликована: Июль 31, 2023

Abstract Aryl fluorides are important structural motifs in many pharmaceuticals. Although the Balz–Schiemann reaction provides an entry to aryl from aryldiazonium tetrafluoroborates, it suffers drawbacks such as long time, high temperature, toxic solvent, gas release, and low functional group tolerance. Here, we describe a general method for synthesis of tetrafluoroborates using piezoelectric material redox catalyst under ball milling conditions presence Selectfluor. This approach effectively addresses aforementioned limitations. Furthermore, can be recycled multiple times. Mechanistic investigations indicate that this fluorination may proceed via radical pathway, Selectfluor plays dual role both source fluorine terminal reductant.

Язык: Английский

Процитировано

29

Mechanical‐Force‐Induced Non‐spontaneous Dehalogenative Deuteration of Aromatic Iodides Enabled by Using Piezoelectric Materials as a Redox Catalyst DOI

Ruiling Qu,

Shan Wan, Xuemei Zhang

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(28)

Опубликована: Апрель 30, 2024

Abstract The development of green and efficient deuteration methods is great significance for various fields such as organic synthesis, analytical chemistry, medicinal chemistry. Herein, we have developed a dehalogenative strategy using piezoelectric materials catalysts in solid‐phase system under ball‐milling conditions. This non‐spontaneous reaction induced by mechanical force. D 2 O can serve both deuterium source an electron donor the transformation, eliminating need additional stoichiometric exogenous reductants. A series (hetero)aryl iodides be transformed into deuterated products with high incorporation. method not only effectively overcomes existing synthetic challenges but also used labelling drug molecules derivatives. Bioactivity experiments molecule suggest that D‐ipriflavone enhances inhibitory effects on osteoclast differentiation BMDMs vitro .

Язык: Английский

Процитировано

11

Intramolecular direct arylation through mechanochemistry: efficient synthesis of corannulene-based peri-annulated curved nanographenes DOI
Zhongbo Zhang, Mihaiela C. Stuparu

Science China Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 6, 2025

Язык: Английский

Процитировано

1

Mechanochemically Induced Cross Dehydrogenative Coupling Reactions under Ball Milling DOI
Ilya N. Egorov, Anindita Mukherjee, Sougata Santra

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(15), С. 2462 - 2478

Опубликована: Июнь 16, 2022

Abstract Cross dehydrogenative coupling (CDC) reactions have become a convenient synthetic strategy for the synthesis of various (het)aromatic scaffolds. In recent times ball milling has emerged as powerful tool to perform in greener way. The current review highlights applications cross under towards useful molecules more efficient and manner. magnified image

Язык: Английский

Процитировано

31

Ball-milling-enabled nickel-catalyzed radical relayed reductive cross-coupling DOI Creative Commons
Chunying Fan, Bobo Wang, Tianle Wu

и другие.

Cell Reports Physical Science, Год журнала: 2024, Номер 5(2), С. 101831 - 101831

Опубликована: Фев. 1, 2024

Nickel-catalyzed radical relayed dicarbofunctionalizations of olefins, utilizing carbon electrophiles as coupling partners, present a powerful strategy for the streamlined construction aliphatic structures. However, traditional solution-phase methods encounter challenges such need bulk solvents, limited long reaction times, and air-/moisture-sensitive reagents. As an alternative strategy, ball-mill-enabled metal-catalyzed cross-coupling reactions have gained attention due to their high reactivity atomic efficiency. While many are single- two-component methodologies, three-component solid-state remain relatively scarce. In this work, we report first, our knowledge, ball-milling-enabled Ni-catalyzed reductive dicarbofunctionalization alkenes. Two distinct readily available electrophiles, Csp2 Csp3 halides, simultaneously installed across variety olefins at room temperature in highly regioselective manner withing 1.5 h. By harnessing benefits ball milling reactions, anticipate further advancements sustainable efficient synthetic methodologies.

Язык: Английский

Процитировано

8

Organic Reactions Enabled by Mechanical Force‐Induced Single Electron Transfer DOI
Ruoxuan Liu,

Xiaochun He,

Tianfen Liu

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер 30(47)

Опубликована: Июнь 18, 2024

Mechanochemical reactions, achieved through milling, grinding, or other mechanical actions, have emerged as a solvent-free alternative to traditional solution-based chemistry. Mechanochemistry not only provides the opportunity eliminate bulk solvent use, reducing waste generation, but also unveils new reaction strategy which enables realization of reactions previously inaccessible in solution. While majority organic facilitated by force traditionally follow two-electron transfer pathways similar their counterparts, field mechanochemically induced single-electron (SET) has witnessed rapid development. This review outlines examples mechanochemical SET process, focusing on reagents that initiate SET, thereby positioning mechanochemistry burgeoning within realm

Язык: Английский

Процитировано

7

Safety Considerations and Proposed Workflow for Laboratory-Scale Chemical Synthesis by Ball Milling DOI Creative Commons

Ian Priestley,

Claudio Battilocchio, Andrei V. Iosub

и другие.

Organic Process Research & Development, Год журнала: 2023, Номер 27(2), С. 269 - 275

Опубликована: Фев. 3, 2023

Chemical reactions that take place in a ball mill and the absence of bulk reaction solvent present different safety profiles to stirred solution reactions. Herein, we describe steps researcher may better ensure they have considered some hazards measures emerge minimize risk themselves their colleagues.

Язык: Английский

Процитировано

14

Mechanochemical Difluoromethylations of Alcohols DOI
Pit van Bonn,

Jinbo Ke,

Christopher Weike

и другие.

CCS Chemistry, Год журнала: 2023, Номер 5(8), С. 1737 - 1744

Опубликована: Май 8, 2023

Difluoromethyl ethers are formed through mechanochemical reactions of alcohols with difluorocarbene in a mixer mill.The protocol could be applied to primary, secondary, and tertiary alcohols, yielding the corresponding products excellent yields (up 99%) after 1 h reaction time at room temperature.The transformations proceeded under solvent-free conditions, followed by product purification filtration, which drastically reduced amount waste generated during process.CsCl + TMSCF 2 Br Solvent-free Pure filtration rt, 1°, 2°, 3°alcohols Mild conditions Operationally simple Difluorocarbene pathway

Язык: Английский

Процитировано

14

Nickel-catalyzed cross-coupling aminations via high-throughput mechanochemistry enabled by resonant acoustic mixing DOI Creative Commons
Alice Nanni,

Deshen Kong,

Chen Zhu

и другие.

Green Chemistry, Год журнала: 2024, Номер 26(14), С. 8341 - 8347

Опубликована: Янв. 1, 2024

Resonant Acoustic Mixing (RAM) allows High Throughput Experimentation (HTE) using commercially available 96-well plates as exemplified by the nickel catalyzed C–N cross coupling of aryl halides with different amine and anilines.

Язык: Английский

Процитировано

6