Enantioselective Remote Alkylation Enabled by Metallaphotoredox Catalysis via Selective C–C Bond Cleavage DOI
Ao Yu,

Ning Wang,

Siyuan Tang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 2212 - 2221

Published: Jan. 23, 2025

Despite recent advances in enantioselective radical coupling with strained cyclic rings, asymmetric reactions triggered by unstrained motifs remain rare. Herein, we report a mild and general strategy for activating diverse set of readily available alcohols the remote site-specific allylic alkylation ketones through combination photoredox-mediated proton-coupled electron transfer chiral chromium catalysis. This newly developed dual catalytic system exhibits extensive applicability, operates under conditions, offers straightforward operation, demonstrates tolerance to functional groups. The open-shell has also been applied late-stage modification complex drug natural product derivatives high levels enantioselectivity.

Language: Английский

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
Iron-Catalyzed Aerobic Carbonylation of Methane via Ligand-to-Metal Charge Transfer Excitation DOI Creative Commons
Hui Pan, Qing An, Binh Khanh

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 6, 2025

The integration of ligand-to-metal charge transfer (LMCT) catalytic paradigms with radical intermediates has transformed the selective functionalization inert C-H bonds, facilitating use nonprecious metal catalysts in demanding transformations. Notably, aerobic carbonylation methane to acetic acid remains formidable due rapid oxidation methyl radicals, producing undesired C1 oxygenates. We present an iron terpyridine catalyst utilizing LMCT achieve exceptional C2/C1 selectivity through synergistic photoexcitation, generation, and carbonylation. Mechanistic studies highlight critical roles Fe(II) Fe-carbonyl complexes bypassing via a rebound-like pathway, unlocking unprecedented efficiency

Language: Английский

Citations

2
Aromatization-driven deconstructive functionalization of spiro dihydroquinazolinones via dual photoredox/nickel catalysis DOI Creative Commons

Hong-Jie Miao,

Jinhua Zhang, Wenke Li

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(23), P. 8993 - 8999

Published: Jan. 1, 2024

The aromatization-driven deconstructive coupling of spiro carbocycles with organic halides via dual photoredox/nickel catalysis is developed. An in-depth mechanism study revealed that this reaction proceeded a radical-metal crossover pathway.

Language: Английский

Citations

15
Satellite-like shielding for dual single-atom catalysis, boosting ampere-level alkaline seawater splitting DOI
Hao Chen, Yanqin Wang, Rong Ding

et al.

Matter, Journal Year: 2024, Volume and Issue: 7(9), P. 3189 - 3204

Published: June 21, 2024

Language: Английский

Citations

13
Photoinduced Selective B–H Activation of nido-Carboranes DOI

Sheng‐Wen Xu,

Hongjian Zhang, Jingkai Xu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7791 - 7802

Published: March 10, 2024

The development of new synthetic methods for B–H bond activation has been an important research area in boron cluster chemistry, which may provide opportunities to broaden the application scope clusters. Herein, we present a reaction strategy direct site-selective functionalization nido-carboranes initiated by photoinduced cage via noncovalent cage···π interaction. As result, nido-carborane radical is generated through single electron transfer from 3D 2D photocatalyst upon irradiation with green light. resulting transient could be directly probed advanced time-resolved EPR technique. In air, subsequent transformations active have led efficient and selective B–N, B–S, B–Se couplings presence N-heterocycles, imines, thioethers, thioamides, selenium ethers. This protocol also facilitates both late-stage modification drugs synthesis nido-carborane-based drug candidates neutron capture therapy (BNCT).

Language: Английский

Citations

12
Enantioselective [2 + 2] Photocycloreversion Enables De Novo Deracemization Synthesis of Cyclobutanes DOI
Jiahao Wang,

Qianqian Fu,

Shanshan Cao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22840 - 22849

Published: Aug. 2, 2024

While photochemical deracemization significantly enhances atom economy by eliminating the necessity for additional oxidants or reductants, laborious presynthesis of substrates from feedstock chemicals is often required, thereby compromising practicality this method. In study, we propose a novel approach known as de novo synthesis, which involves direct utilization simple undergoing both transformation and reversible transformation. The efficient enantiocontrol chiral catalysts in latter process establishes an effective platform deracemization. This alternative practical to address challenges asymmetric photocatalysis has been successfully demonstrated photosensitized synthesis azaarene-functionalized cyclobutanes featuring three stereocenters, including all-carbon quaternary center. By exclusively employing suitable catalyst enable kinetically controlled [2 + 2] photocycloreversion, pave creative path toward achieving more cost-effective

Language: Английский

Citations

10
Photoexcited Palladium-Catalyzed Deracemization of Allenes DOI

Changhua Song,

Xiangbin Bai,

Bo Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(30), P. 21137 - 21146

Published: July 18, 2024

The different enantiomers of specific chiral molecules frequently exhibit disparate biological, physiological, or pharmacological properties. Therefore, the efficient synthesis single is particular importance not only to pharmaceutical sector but also other industrial sectors, such as agrochemical and fine chemical industries. Deracemization, a process during which racemic mixture converted into nonracemic product with 100% atom economy theoretical yield, most straightforward method access enantioenriched challenging task due decrease in entropy microscopic reversibility. Axially allenes bear distinctive structure two orthogonal cumulative π-systems are acknowledged synthetically versatile synthons organic synthesis. selective creation axially high optical purity under mild reaction conditions has always been very popular hot topic remains challenging. Herein, photoexcited palladium-catalyzed deracemization nonprefunctionalized disubstituted disclosed. This provides an economical strategy accommodate broad scope good enantioselectivities yields (53 examples, up 96% yield 95% ee). use suitable palladium complex visible light irradiation essential factor achieving this transformation. A metal-to-ligand charge transfer mechanism was proposed based on control experiments density functional theory calculations. Quantum mechanical studies implicate dual modes asymmetric induction behind our new protocol: (1) sterically controlled stereoselective binding one allene enantiomer ground-state (2) facile, noncovalent interaction-driven excited-state isomerization toward opposite enantiomer. success newly established photochemical should provide inspiration for expansion multisubstituted will open mode enantioselective catalysis.

Language: Английский

Citations

9
Ligand-to-Metal Charge Transfer (LMCT) Catalysis: Harnessing Simple Cerium Catalysts for Selective Functionalization of Inert C–H and C–C Bonds DOI Creative Commons
Qing An, Liang Chang, Hui Pan

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 18, 2024

ConspectusChemists have long pursued harnessing light energy and photoexcitation processes for synthetic transformations. Ligand-to-metal charge transfer (LMCT) in high-valent metal complexes often triggers bond homolysis, generating oxidized ligand-centered radicals reduced centers. While photoinduced oxidative activations can be enabled, this process, typically seen as photochemical decomposition, remains underexplored catalytic applications. To mitigate decomposition during LMCT excitation, we developed a cycle integrating situ coordination, LMCT, ligand homolysis to activate ligated alcohols transiently into alkoxy radicals. This approach leverages Ce(IV) excitation highly reactive radical intermediates selective functionalizations of C(sp

Language: Английский

Citations

9
Revealing the nature of covalently tethered distonic radical anions in the generation of heteroatom-centered radicals: evidence for the polarity-matching PCET pathway DOI Creative Commons
Kang Fu,

Xihui Yang,

Zhiyou Yu

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(31), P. 12398 - 12409

Published: Jan. 1, 2024

The philicity-regulation and PCET mechanism of tether-tunable distonic radical anion-mediated generation heteroatom-centered radicals has been explored via experimental theoretical investigations.

Language: Английский

Citations

8
A De Novo Metalloenzyme for Cerium Photoredox Catalysis DOI Creative Commons
Andreas Klein, Florian Leiss-Maier, Rahel Mühlhofer

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(38), P. 25976 - 25985

Published: Aug. 8, 2024

Cerium photoredox catalysis has emerged as a powerful strategy to activate molecules under mild conditions. Radical intermediates are formed using visible light and simple complexes of the earth-abundant lanthanide. Here, we report an artificial photoenzyme enabling this chemistry inside protein. We utilize de novo designed protein scaffold that tightly binds lanthanide ions in its central cavity. Upon visible-light irradiation, cerium-dependent enzyme catalyzes radical C-C bond cleavage 1,2-diols aqueous solution. Protein engineering led variants with improved photostability metal binding behavior. The cleaves range aromatic aliphatic substrates, including lignin surrogates. Surface display on

Language: Английский

Citations

8