Mechanochemical Conditions for Intramolecular N–O Couplings via Rhodium Nitrenoids Generated from N‐Acyl Sulfonimidamides DOI Creative Commons

Shulei Pan,

Peng Wu,

Dimitra Bampi

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 9, 2024

Abstract Starting from N ‐acyl sulfonimidamides, mechanochemically generated rhodium nitrenoids undergo intramolecular N−O couplings to provide unprecedented 1,3,2,4‐oxathiadiazole 3‐oxides in good excellent yields. The cyclization proceeds efficiently with a catalyst loading of only 0.5 mol % the presence phenyliodine(III) diacetate (PIDA) as oxidant. Neither an inert atmosphere nor additional heating is required this solvent‐free procedure. Under heat or blue light, newly formed five‐membered heterocycles function nitrene precursors reacting sulfoxides exemplified by imidation dimethyl sulfoxide.

Language: Английский

Mechanoredox‐Catalyzed Organic Synthesis with Piezoelectric Materials: Quo Vadis? DOI Open Access
Hanggara Sudrajat, Hsien‐Yi Hsu, François Jérôme

et al.

ChemCatChem, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 24, 2025

Abstract Piezoelectric materials offer great promise due to their ability generate electric fields under mechanical stress, producing surface charges that drive otherwise kinetically sluggish redox reactions. The strained surfaces of these provide a unique advantage in controlling product selectivity and enabling reaction pathways are unattainable with conventional methods. This perspective highlights advancements, challenges, the future potential piezoelectric synthetic organic chemistry, focus on designing optimized for piezocatalyzed synthesis. Piezocatalysis is industrially relevant because its operational simplicity, mild, gram scale synthesis reusable catalysts, minimal solvent use, air tolerant conditions. It involves cycles facilitate one electron events without requiring light exposure or electrical bias. Despite significant progress, many fundamental aspects yet be fully understood. One example correlation between piezoelectricity catalytic activity, which not always linear, as demonstrated by comparison tetragonal cubic BaTiO₃. While BaTiO₃ piezoelectric, it shows excellent activity certain reactions such arylation, dicarbonylation, cyclization mechanochemical conditions comparable Considering all aspects, this aims stimulate discussion advance promising field right direction.

Language: Английский

Citations

0

Productive Chemistry Induced by Mechanochemically Generated Macroradicals DOI Creative Commons
Chenxu Wang, Cai‐Li Sun, Roman Boulatov

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(77), P. 10629 - 10641

Published: Jan. 1, 2024

Large or repeated mechanical loads degrade polymeric materials by accelerating chain fragmentation. This mechanochemical backbone fracture usually occurs homolysis of otherwise inert C-C, C-O and C-S bonds, generating highly reactive macroradicals. Because is detrimental on its own the resulting macroradicals can initiate damaging reaction cascades, a major thrust in contemporary polymer mechanochemistry to suppress it, release "hidden length" that dissipates local molecular strain. Here we summarize an emerging complementary strategy channelling mechanochemically generated cascades form new load-bearing chemical which enables self-healing self-strengthening, and/or generate mechanofluorescence, could yield detailed quantitative understanding how material-failure-inducing macroscopic distribute across network. We aim identify generalizable lessons derivable from reported implementations this outline key challenges adapting it diverse loading scenarios.

Language: Английский

Citations

2

Mechanochemical Conditions for Intramolecular N–O Couplings via Rhodium Nitrenoids Generated from N‐Acyl Sulfonimidamides DOI Creative Commons

Shulei Pan,

Peng Wu,

Dimitra Bampi

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 9, 2024

Abstract Starting from N ‐acyl sulfonimidamides, mechanochemically generated rhodium nitrenoids undergo intramolecular N−O couplings to provide unprecedented 1,3,2,4‐oxathiadiazole 3‐oxides in good excellent yields. The cyclization proceeds efficiently with a catalyst loading of only 0.5 mol % the presence phenyliodine(III) diacetate (PIDA) as oxidant. Neither an inert atmosphere nor additional heating is required this solvent‐free procedure. Under heat or blue light, newly formed five‐membered heterocycles function nitrene precursors reacting sulfoxides exemplified by imidation dimethyl sulfoxide.

Language: Английский

Citations

2

Calcium Carbide (CaC2) as a C2‐Synthon by Mechanochemistry DOI
Alejandro Cortés‐Lobo, José G. Hernández

ChemPlusChem, Journal Year: 2024, Volume and Issue: unknown

Published: May 31, 2024

Abstract Mechanochemical reactions by ball milling have opened new avenues in chemical synthesis. Particularly, mechanochemistry has facilitated the reaction of insoluble materials to simplify stablished synthetic protocols and develop ones. One notable application involves use calcium carbide (CaC 2 ) as a C ‐synthon through mechanochemistry, which offered more practical alternative incorporate ‐units compared conventional highly flammable gaseous acetylene. For example, milling, acetylenic anions [C ] 2− found CaC been harnessed for synthesis diverse functional carbon well discrete organic molecules. This Concept aims contribute conceptualization this innovative approach while highlighting both its advantages challenges inherent .

Language: Английский

Citations

1

Mechanochemical Radical Transformations in Organic Synthesis DOI

Jon Sperry,

Sahra Sheikhaleslami

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 22, 2024

Abstract Organic synthesis has historically relied on solution‐phase, polar transformations to forge new bonds. However, this paradigm is evolving, propelled by the rapid evolution of radical chemistry. Additionally, organic witnessing a simultaneous resurgence in mechanochemistry, formation bonds solid‐state, further contributing shift status quo. The aforementioned advances chemistry have predominantly occurred solution phase, while majority mechanochemical feature transformations. Herein, we discuss rapidly advancing area synthesis: reactions. Solid‐state reactions offer improved green metrics, better reaction outcomes, and access intermediates products that are difficult or impossible reach solution. This review explores these context small molecule synthesis, from early findings current state‐of‐the‐art, underscoring pivotal role solid‐state likely play sustainable chemical synthesis.

Language: Английский

Citations

1

Grinding and the anisotropic environment: influences on the diastereoselective formation of Group 15 allyl complexes DOI Creative Commons
Lauren E. Wenger, Timothy P. Hanusa

RSC Mechanochemistry, Journal Year: 2024, Volume and Issue: 1(3), P. 235 - 243

Published: Jan. 1, 2024

Layered solids (AsI 3 , SbCl ) can serve as templates for diastereomer formation, and mechanochemical variables shift their ratios.

Language: Английский

Citations

0

Mechanochemical Synthesis of a Sodium Anion Complex [Na+(2,2,2-cryptand)Na] and Studies of Its Reactivity: Two-Electron and One-Electron Reductions DOI Creative Commons
Nathan Davison, Jack M. Hemingway, Corinne Wills

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(32), P. 15247 - 15258

Published: July 29, 2024

Group 1 metal molecular chemistry is dominated by a +1 oxidation state, while 0 state widespread in the metals. A more exotic, yet still available, of group -1, i.e., alkalide. Reported as early 1970s, alkalides appear every modern inorganic textbook an iconic chemical curiosity, their reactivity remains unexplored. This due to synthetic hurdles. In this work, we report first facile synthesis archetypical alkalide complex, [Na

Language: Английский

Citations

0

Efficient Synthesis of (S)-Aromatic Epoxides by Coupling Mechanochemical Synthesis and Biocatalysis Technology DOI
Ling Jiang,

Hailing Yang,

Qiong Xiao

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(37), P. 13774 - 13782

Published: Sept. 3, 2024

(S)-aromatic epoxides are of great importance in the production pharmaceuticals and biologically active natural products. Consequently, developing efficient, ecofriendly, economical methods for continues to be tremendous interest organic synthesis. Herein, we report a novel protocol efficient synthesis by coupling mechanochemical biocatalysis from commercially available cheap materials. The first step process is halogenation aromatic ketones with N-halosuccinimides (NXS) under ball-milling conditions form α-haloaromatic ketones. This followed one-pot asymmetric bioreduction–cyclization sequence affording various good yields, which pure enough without further purification. Compared traditional chemical approaches, this mechano-biocatalytic has prominent advantages, including inexpensive starting materials, short reaction time, simplicity operation, environmental benignity, broad substrate spectrum, excellent enantioselectivities, easy isolation

Language: Английский

Citations

0

Mechanochemical Synthesis of Molecular Chemoreceptors DOI Creative Commons
Jakub S. Cyniak, Artur Kasprzak

ACS Omega, Journal Year: 2024, Volume and Issue: 9(50), P. 48870 - 48883

Published: Dec. 6, 2024

The design of environmentally friendly methods for synthesizing molecular receptors is an expanding area within applied organic chemistry. This work systematically summarizes advances in the mechanochemical synthesis chemoreceptors. It discusses key achievements related to chemoreceptors containing azine, Schiff base, thiosemicarbazone, hydrazone, rhodamine 6G, imide, or amide moieties. Additionally, it highlights application potential mechanochemically synthesized recognition ions and small molecules, along with a discussion mechanisms detection processes.

Language: Английский

Citations

0

Mechanochemical Ball Milling Approach to C(sp3)‐H Functionalization of 8‐Methylquinolines DOI Creative Commons
N. Narayanan, Michael Schnürch

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 23, 2024

Abstract A mechanochemical, highly regioselective rhodium(III)‐catalyzed C─H methylation of 8‐methylquinolines is reported. The method reported in this study, often solvent‐free or uses minimal solvent (liquid assisted grinding), operates without external heating under mild reaction conditions, demonstrating tolerance for various functional groups. Moreover, the time significantly reduced compared to solvent‐based variant. Notably, can be carried out using a pestle and mortar instead ball milling as well, highlighting operational simplicity approach achieving challenging C(sp 3 )‐H activation more sustainable conditions.

Language: Английский

Citations

0