Aerobic mechanochemical reversible-deactivation radical polymerization DOI Creative Commons
Haoyang Feng, Zhe Chen,

Lei Li

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: July 22, 2024

Abstract Polymer materials suffer mechano-oxidative deterioration or degradation in the presence of molecular oxygen and mechanical forces. In contrast, aerobic biological activities combined with stimulus promote tissue regeneration repair various organs. A synthetic approach which energy synergistically initiate polymerization will afford similar robustness polymeric materials. Herein, mechanochemical reversible-deactivation radical was developed by design an organic mechano-labile initiator converts into activators response to ball milling, enabling reaction proceed air low-energy input, operative simplicity, avoidance potentially harmful solvents. addition, this not only complements existing methods access well-defined polymers but also has been successfully employed for controlled (meth)acrylates, styrenic monomers solid acrylamides as well synthesis polymer/perovskite hybrids without solvent at room temperature are inaccessible other means.

Language: Английский

Iron-Catalyzed C(Sp3)–H Borylation, Thiolation, and Sulfinylation Enabled by Photoinduced Ligand-to-Metal Charge Transfer DOI
Jia‐Lin Tu,

Ao-Men Hu,

Lin Guo

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(13), P. 7600 - 7611

Published: March 23, 2023

Catalytic C(sp3)-H functionalization has provided enormous opportunities to construct organic molecules, facilitating the derivatization of complex pharmaceutical compounds. Within this framework, direct hydrogen atom transfer (HAT) photocatalysis becomes an appealing approach goal. However, viable substrates utilized in these protocols are limited, and site selectivity shows preference activated thermodynamically favored bonds. Herein, we describe development undirected iron-catalyzed borylation, thiolation, sulfinylation reactions enabled by photoinduced ligand-to-metal charge (LMCT) process. These exhibit remarkably broad substrate scope (>150 examples total), most importantly, all three show unconventional regioselectivity, with occurrence preferentially at distal methyl position. The procedures operationally simple readily scalable provide access high-value products from hydrocarbons one step. Mechanistic studies control experiments indicate that afforded is not only relevant HAT species but also largely affected use boron- sulfone-based radical acceptors.

Language: Английский

Citations

117
Resurgence and advancement of photochemical hydrogen atom transfer processes in selective alkane functionalizations DOI Creative Commons
Liang Chang, Shun Wang, Qing An

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(25), P. 6841 - 6859

Published: Jan. 1, 2023

The selective functionalization of alkanes has long been recognized as a prominent challenge and an arduous task in organic synthesis. Hydrogen atom transfer (HAT) processes enable the direct generation reactive alkyl radicals from feedstock have successfully employed industrial applications such methane chlorination process,

Language: Английский

Citations

70
Multiplicative enhancement of stereoenrichment by a single catalyst for deracemization of alcohols DOI
Lu Wen, Jia Ding, Lingfei Duan

et al.

Science, Journal Year: 2023, Volume and Issue: 382(6669), P. 458 - 464

Published: Oct. 26, 2023

Stereochemical enrichment of a racemic mixture by deracemization must overcome unfavorable entropic effects as well the principle microscopic reversibility; recently, photochemical reaction pathways unveiled energetic input light have led to innovations toward this end, most often ablation stereogenic C(sp3)-H bond. We report photochemically driven protocol in which single chiral catalyst two mechanistically different steps, C-C bond cleavage and formation, achieve multiplicative enhancement stereoinduction, leads high levels stereoselectivity. Ligand-to-metal charge transfer excitation titanium coordinated phosphoric acid or bisoxazoline efficiently enriches alcohols that feature adjacent fully substituted centers enantiomeric ratios up 99:1. Mechanistic investigations support pathway sequential radical-mediated scission formation through common prochiral intermediate reveal that, although overall stereoenrichment is high, selectivity each individual step moderate.

Language: Английский

Citations

63
Scalability of advanced oxidation processes (AOPs) in industrial applications: A review DOI Creative Commons
Parvez Mahbub, Mikel Duke

Journal of Environmental Management, Journal Year: 2023, Volume and Issue: 345, P. 118861 - 118861

Published: Aug. 29, 2023

Disinfection and decontamination of water by application oxidisers is an essential treatment step across numerous industrial sectors including potable supply industry waste management, however, could be greatly enhanced if operated as advanced oxidation processes (AOPs). AOPs destroy contaminants pathogens uniquely harnessing radical chemistry. Despite offer great practical opportunities, no reviews to date have highlighted the critical AOP virtues that facilitate AOPs' scale up under growing demand. Hence, this review analyses parameters such oxidant conversion efficiency, batch mode vs continuous-flow systems, location production, delivery micro-/mesoporous structures process costs assist translation progressing developments into their large-scale applications. Additionally, state art analysed for various inducing radical/oxidiser measurement techniques half-lives with a view identify radicals/oxidisers are suitable in-situ production. It concluded radicals short hydroxyl (10-4 μsec) sulfate (30-40 need produced via reactors effective transport dosing. Meanwhile, longer ozone (7-10 min), hydrogen peroxide (stable several hours), hypochlorous acid (10 min -17 h) applied through reactor systems due relatively stability during transportation Complex costly synthesis well cytotoxicity many limit use in scaling AOPs, particularly immobilising delivering short-lived point Overall, using safe biocompatible structures, efficiency design portability priority areas development industry.

Language: Английский

Citations

60
Terminal C(sp 3 )–H borylation through intermolecular radical sampling DOI
Miao Wang, Yahao Huang, Peng Hu

et al.

Science, Journal Year: 2024, Volume and Issue: 383(6682), P. 537 - 544

Published: Feb. 1, 2024

Hydrogen atom transfer (HAT) processes can overcome the strong bond dissociation energies (BDEs) of inert C(sp

Language: Английский

Citations

34
Site- and enantioselective allylic and propargylic C–H oxidation enabled by copper-based biomimetic catalysis DOI
Honggang Zhang,

Ying Zhou,

Tilong Yang

et al.

Nature Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

Language: Английский

Citations

4
N‐Hydroxyphthalimide/TiO2 Catalyzed Addition of Ethers, Alkylarenes and Aldehydes to Azodicarboxylates under Visible Light DOI Open Access
Elena R. Lopat’eva, Igor B. Krylov, Alexander O. Terent’ev

et al.

Chemistry - A European Journal, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 31, 2025

The addition of carbon-centered radicals to double bonds is one the most atom-efficient approaches formation new C-C or C-heteroatom bonds. Existing for generation often require elevated temperatures, UV radiation expensive transition metal catalysts. In this work, a photocatalytic system based on heterogeneous TiO2 catalyst and redox organocatalyst N-hydroxyphthalimide proposed from C(sp3)-H substrates aldehydes at room temperature under visible light irradiation. developed approach was successfully applied ethers, alkylarenes azodicarboxylates. Titanium oxide acts as photocatalyst, producing phthalimide-N-oxyl N-hydroxyphthalimide, thereby enabling organocatalytic process in solution. Phthalimide-N-oxyl act catalytically active species that cleave C-H form radicals.

Language: Английский

Citations

2
Copper-Mediated Dehydrogenative C(sp3)–H Borylation of Alkanes DOI Creative Commons
Ruocheng Sang, Wangyujing Han, Hanwen Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15207 - 15217

Published: July 6, 2023

Borylations of inert carbon-hydrogen bonds are highly useful for transforming feedstock chemicals into versatile organoboron reagents. Catalysis these reactions has historically relied on precious-metal complexes, which promote dehydrogenative borylations with diboron reagents under oxidant-free conditions. Recently, photoinduced radical-mediated involving hydrogen atom transfer pathways have emerged as attractive alternatives because they provide complimentary regioselectivities and proceed metal-free However, net oxidative processes require stoichiometric oxidants therefore cannot compete the high economy their precious-metal-catalyzed counterparts. Herein, we report that CuCl2 catalyzes radical-mediated, C(sp3)-H alkanes bis(catecholato)diboron This is a result an unexpected dual role copper catalyst, promotes oxidation reagent to generate electrophilic bis-boryloxide acts effective borylating agent in subsequent redox-neutral photocatalytic C-H borylations.

Language: Английский

Citations

38
Photoelectrochemical oxidative C(sp3)−H borylation of unactivated hydrocarbons DOI Creative Commons
Ping‐Fu Zhong, Jia‐Lin Tu,

Yating Zhao

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Oct. 16, 2023

Organoboron compounds are of high significance in organic synthesis due to the unique versatility boryl substituents access further modifications. The demand for incorporation moieties into molecular structures has witnessed significant progress, particularly C(sp3)-H borylation hydrocarbons. Taking advantage special characteristics photo/electrochemistry, we herein describe development an oxidative reaction under metal- and oxidant-free conditions, enabled by photoelectrochemical strategy. exhibits broad substrate scope (>57 examples), includes use simple alkanes, halides, silanes, ketones, esters nitriles as viable substrates. Notably, unconventional regioselectivity is achieved, with coupling site selectively located distal methyl group. Our method operationally easily scalable, offers a feasible approach one-step high-value organoboron building blocks from hydrocarbons, which would provide ample opportunities drug discovery.

Language: Английский

Citations

37
Electrophotochemical Metal‐Catalyzed Enantioselective Decarboxylative Cyanation DOI
Kai Yang, Yukang Wang, Sanzhong Luo

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(24)

Published: Jan. 13, 2023

Abstract In contrast to the rapid growth of electrophotocatalysis in recent years, enantioselective catalytic reactions powered by this unique methodology remain rare. work, we report an electrophotochemical metal‐catalyzed protocol for direct asymmetric decarboxylative cyanation aliphatic carboxylic acids. The synergistic merging cerium catalysis and electrochemical copper permits mild reaction conditions formation utilization key carbon centered radicals combining power light electrical energy. Electrophotochemical enables radical decarboxylation produce alkyl radicals, which could be effectively intercepted construction C−CN bonds a highly stereoselective fashion. This environmentally benign method smoothly converts diverse array arylacetic acids into corresponding nitriles good yields enantioselectivities without using chemical oxidants or pre‐functionalization acid substrates can readily scaled up.

Language: Английский

Citations

30