Lewis and Brønsted Acids Synergy in Photocatalytic Aerobic Alcohol Oxidations DOI Open Access

Dexi Yu,

Junhua Zou, Lingdong Zeng

et al.

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 31, 2025

Photocatalytic chemical transformations for green organic synthesis has attracted much interest. However, their development is greatly hampered by the lack of sufficient reactive sites on photocatalyst surface adsorption and activation substrate molecules. Herein, we demonstrate that introduction well-defined Lewis Brønsted acid coexisting TiO2 (SO4 2-/N-TiO2) creates abundant active photoredox reactions. The electron-deficient supply coordinatively unsaturated to adsorb molecular oxygen, are liable donate protons form hydrogen bonds with OH groups alcohols like benzyl alcohol (BA). These coexistent result in a strong synergistic effect photocatalytic aerobic oxidation BA. For example, conversion BA benzaldehyde was found be 88.6 %, being higher than those pristine (14.7 %), N-doped (N-TiO2, 24.6 sulfated 2-/ TiO2, 35.4 even sum. apparent quantum efficiency (AQE) determined 58.1 % at 365 nm 12.9 420 over SO4 2-/N-TiO2. This strategy create effective acids catalyst surfaces enables us apply it other semiconducting transformations.

Language: Английский

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

66
Radical Hydrocarboxylation of Unactivated Alkenes via Photocatalytic Formate Activation DOI
Sara N. Alektiar, Jimin Han, Yun Dang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 10991 - 10997

Published: May 15, 2023

Herein we disclose a strategy to promote the hydrocarboxylation of unactivated alkenes using photochemical activation formate salts. We illustrate that an alternative initiation mechanism circumvents limitations prior approaches and enables this challenging substrate class. Specifically, found accessing requisite thiyl radical initiator without exogenous chromophore eliminates major byproducts have plagued attempts exploit similar reactivity for alkene substrates. This redox-neutral method is technically simple execute effective across broad range Feedstock alkenes, such as ethylene, are hydrocarboxylated at ambient temperature pressure. A series cyclization experiments indicate how described in report can be diverted by more complex processes.

Language: Английский

Citations

62
Synthetic Advantages of Defluorinative C−F Bond Functionalization DOI Creative Commons
Leidy V. Hooker, Jeffrey S. Bandar

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Aug. 22, 2023

Abstract Much progress has been made in the development of methods to both create compounds that contain C−F bonds and functionalize bonds. As such, are becoming common versatile synthetic functional handles. This review summarizes advantages defluorinative functionalization reactions for small molecule synthesis. The coverage is organized by type carbon framework fluorine attached mono‐ polyfluorinated motifs. main challenges, opportunities advances discussed each class organofluorine. Most text focuses on case studies illustrate how defluorofunctionalization can improve routes targets or properties enable unique mechanisms reactions. broader goal showcase incorporating exploiting design routes, improvement specific advent new methods.

Language: Английский

Citations

57
Free Carboxylic Acids: The Trend of Radical Decarboxylative Functionalization DOI
Liubo Li, Yan Yao, Niankai Fu

et al.

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(21)

Published: April 7, 2023

Abstract The exceptional versatility of carboxylic acids has been extensively exploited in organic synthesis across several decades. There a recent upsurge radical decarboxylative transformations. process can be initiated under mild conditions, and the resultant radicals have orthogonal reactivities to closed‐shell species, thus providing immense opportunities for streamlining novel reactions. use free is most desirable owing its high atom step economy. Aiming demonstrate attractiveness strategy inspire chemists tackle existing challenges, this review outlines advances on functionalization acids.

Language: Английский

Citations

54
Iron-mediated modular decarboxylative cross-nucleophile coupling DOI Creative Commons
Grace A. Lutovsky, Samuel N. Gockel, Mark W. Bundesmann

et al.

Chem, Journal Year: 2023, Volume and Issue: 9(6), P. 1610 - 1621

Published: May 4, 2023

Language: Английский

Citations

50
Direct Decarboxylation of Trifluoroacetates Enabled by Iron Photocatalysis** DOI Creative Commons
Sara Fernández‐García, Veronika O. Chantzakou, Francisco Juliá‐Hernández

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(5)

Published: Dec. 13, 2023

Trifluoroacetates are the most abundant and accessible sources of trifluoromethyl groups, which key components in pharmaceuticals agrochemicals. The generation reactive radicals from trifluoroacetates requires their decarboxylation, is hampered by high oxidation potential. This constitutes a major challenge for redox-based methods, because need to pair redox potentials with trifluoroacetate. Here we report strategy based on iron photocatalysis promote direct photodecarboxylation that displays reactivity features escape limitations. Our synthetic design has enabled use trifluoromethylation more easily oxidizable organic substrates, offering new opportunities late-stage derivatization campaigns using chemical feedstocks, Earth-abundant catalysts, visible-light.

Language: Английский

Citations

49
Alcohol-alcohol cross-coupling enabled by S H 2 radical sorting DOI
Ruizhe Chen, Nicholas E. Intermaggio, Jiaxin Xie

et al.

Science, Journal Year: 2024, Volume and Issue: 383(6689), P. 1350 - 1357

Published: March 21, 2024

Alcohols represent a functional group class with unparalleled abundance and structural diversity. In an era of chemical synthesis that prioritizes reducing time to target maximizing exploration space, harnessing these building blocks for carbon-carbon bond-forming reactions is key goal in organic chemistry. particular, leveraging single activation mode form new C(sp

Language: Английский

Citations

45
Engaging Alkenes in Metallaphotoredox: A Triple Catalytic, Radical Sorting Approach to Olefin-Alcohol Cross-Coupling DOI
Qinyan Cai, Iona M. McWhinnie, Nathan W. Dow

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(18), P. 12300 - 12309

Published: April 24, 2024

Metallaphotoredox cross-coupling is a well-established strategy for generating clinically privileged aliphatic scaffolds via single-electron reactivity. Correspondingly, expanding metallaphotoredox to encompass new C(

Language: Английский

Citations

19
Challenges and Future Perspectives in Photocatalysis: Conclusions from an Interdisciplinary Workshop DOI Creative Commons
Sebastian B. Beil, Sylvestre Bonnet, Carla Casadevall

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(8), P. 2746 - 2766

Published: Aug. 8, 2024

Photocatalysis is a versatile and rapidly developing field with applications spanning artificial photosynthesis, photo-biocatalysis, photoredox catalysis in solution or supramolecular structures, utilization of abundant metals organocatalysts, sustainable synthesis, plastic degradation. In this Perspective, we summarize conclusions from an interdisciplinary workshop young principal investigators held at the Lorentz Center Leiden March 2023. We explore how diverse fields within photocatalysis can benefit one another. delve into intricate interplay between these subdisciplines, by highlighting unique challenges opportunities presented each multidisciplinary approach drive innovation lead to solutions for future. Advanced collaboration knowledge exchange across domains further enhance potential photocatalysis. Artificial photosynthesis has become promising technology solar fuel generation, instance, via water splitting CO

Language: Английский

Citations

17
Ligand-Enabled “Two-in-One” Metallaphotocatalytic Cross Couplings DOI
Jianbin Li, Ding Zhang, Zheng Hu

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1635 - 1654

Published: Jan. 15, 2025

Metallaphotoredox cross coupling (MCC) is ranking among the most advanced synthetic methodology as it can access chemical space that difficult to attain under conventional conditions. Earlier developed MCC mandates an independent transition metal catalyst and respective photocatalyst, thus constituting a dual catalytic manifold. Complementarily, paradigm-shifting metallaphotoredox strategy capitalizes on single photoreactive complex emerging, which brings not only operational simplification but also unexpected mechanistic insights. This perspective compiled recent advances in monocatalytic couplings categorized them based ligands confer distinct photoreactivities various mechanisms. To this end, ligand-enabled oxidative addition, transmetalation, reductive elimination other radical-involving pathways were summarized with notable examples. In way, we wish provide handy guideline for readers who are interested emerging field inspire more future endeavors MCCs beyond.

Language: Английский

Citations

3