Decarboxylative sulfoximination of benzoic acids enabled by photoinduced ligand-to-copper charge transfer DOI Creative Commons
Peng Xu, Wanqi Su, Tobias Ritter

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(45), P. 13611 - 13616

Published: Jan. 1, 2022

Sulfoximines are synthetically important scaffolds and serve roles in drug discovery. Currently, there is no solution to decarboxylative sulfoximination of benzoic acids; although thoroughly investigated, limited substrate scope harsh reaction conditions still hold back traditional thermal aromatic functionalization. Herein, we realize the first acids via photo-induced ligand copper charge transfer (copper-LMCT)-enabled carbometalation. The transformation proceeds under mild conditions, has a broad scope, can be applied late-stage functionalization complex small molecules.

Language: Английский

Photocatalytic Production of Syngas from Biomass DOI
Min Wang, Hongru Zhou, Feng Wang

et al.

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(9), P. 1057 - 1069

Published: April 12, 2023

ConspectusAs a renewable solar energy and carbon carrier, biomass exploration has received global attention. Photocatalytic valorization of into fuels chemicals is promising sustainable method for future chemical production. Photocatalysis the potential to accomplish reactions under ambient conditions due unique reaction mechanisms involving photoinduced charge carriers recently been recognized as an efficient feasible technology conversion. Biomass widely used sacrificial agent scavenge holes in photocatalytic hydrogen evolution, eventually degraded CO2 with minor amount CO. The generation CO instead more economical but also challenge photoreforming conditions.This new research direction, while until now there still lack comprehensive review article summarize provide prospects this topic. This Account will highlight our contributions direction reforming syngas (CO + H2). In 2020, we first reported conversion biopolyols sugars by employing defect-rich Cu-TiO2 nanorod photocatalyst found that formic acid key intermediate Further study revealed facet-dependent electron-trapping state on anatase TiO2 affect dehydration activity intermediates regulating electron transfer process during reaction, selective FA or from was achieved via exposing (100) (101) facets, respectively. Visible light-driven further over CdS-based photocatalyst. Sulfate modification CdS ([SO4]/CdS) constructed proton acceptor, thus efficiently facilitating proton-coupled process. Besides, put forward oxygen-controlled strategy increase rate without significant decrease selectivity controlling O2/substrate ratio. Based system, Z-scheme CdS@g-C3N4 core-shell structure CdO-CdS semicoherent interface were created facilitate enhance O2 activation, increasing rate. Moreover, developed photoelectrochemical approach separately produce H2 biomass. Nitrogen doping hexagonal WO3 nanowire array photoanode. built-in electric field generated nitrogen promoted transfer, hence improving efficiency PEC sugars. systematically analyze challenges route reforming, factors affecting give insight design systems.

Language: Английский

Citations

63
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

61
Electrochemically Driven Hydrogen Atom Transfer Catalysis: A Tool for C(sp3)/Si–H Functionalization and Hydrofunctionalization of Alkenes DOI Creative Commons
Sheng Zhang, Michael Findlater

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8731 - 8751

Published: June 16, 2023

Electrochemically driven hydrogen atom transfer (HAT) catalysis provides a complementary approach for the transformation of redox-inactive substrates that would be inaccessible to conventional electron (ET) catalysis. Moreover, electrochemically HAT could promote organic transformations with either abstraction or donation as key step. It versatile and effective tool direct functionalization C(sp3)–H/Si–H bonds hydrofunctionalization alkenes. Despite these attractive properties, has been largely overlooked due lack understanding both catalytic mechanism how catalyst selection should occur. In this Review, we give an overview applications in The mechanistic pathways, physical properties mediators, state-of-the-art examples are described discussed.

Language: Английский

Citations

46
Recent Advances in Electron Donor‐Acceptor (EDA)‐Complex Reactions involving Quaternary Pyridinium Derivatives DOI

Barakha Saxena,

Roshan I. Patel,

Anuj Sharma

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(10), P. 1538 - 1564

Published: March 6, 2023

Abstract Quaternary pyridinium compounds are valuable intermediates in organic synthesis, which have gained immense popularity the synthetic community. The application of transition metal or photoredox catalysis transforming quaternary into various C−C and C−X bonds is well established. A majority these methods require high temperatures, expansive catalysts, delicate conditions for successful execution. On other hand, use metal‐free photocatalysis‐free strategies constructing using derivatives has been sought‐after. In this context, electron‐donor‐acceptor (EDA)‐complex reactions emerged as a state‐of‐the‐art methodology, do not any photocatalyst their EDA‐complex photochemistry takes advantage electron‐acceptor ability derivatives, can quickly generate radical precursor via deaminative process. These newly generated useful several transformations. We hereby, review, discuss an area major progress mediated involving with mechanism, substrate scope, limitations. magnified image

Language: Английский

Citations

43
Azolation of Benzylic C–H Bonds via Photoredox-Catalyzed Carbocation Generation DOI
Mrinmoy Das,

Leila Zamani,

Christopher Bratcher

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 3861 - 3868

Published: Feb. 9, 2023

A visible-light photoredox-catalyzed method is reported that enables the coupling between benzylic C-H substrates and N-H azoles. Classically, medicinally relevant

Language: Английский

Citations

42
Single-Electron Oxidation-Initiated Enantioselective Hydrosulfonylation of Olefins Enabled by Photoenzymatic Catalysis DOI

Qinglong Shi,

Xiu‐Wen Kang, Zhiyong Liu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2748 - 2756

Published: Jan. 12, 2024

Controlling the enantioselectivity of hydrogen atom transfer (HAT) reactions has been a long-standing synthetic challenge. While recent advances on photoenzymatic catalysis have demonstrated great potential non-natural photoenzymes, all transformations are initiated by single-electron reduction substrate, with only one notable exception. Herein, we report an oxidation-initiated enantioselective hydrosulfonylation olefins using novel mutant gluconobacter ene-reductase (GluER-W100F-W342F). Compared to known systems, our approach does not rely formation electron donor–acceptor complex between substrates and enzyme cofactor simplifies reaction system obviating addition regeneration mixture. More importantly, GluER variant exhibits high reactivity broad substrate scope. Mechanistic studies support proposed mechanism reveal that tyrosine-mediated HAT process is involved.

Language: Английский

Citations

35
Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions DOI

Adam Cook,

Stephen G. Newman

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(9), P. 6078 - 6144

Published: April 17, 2024

Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods their functionalization require them to first be converted into a more activated derivative, while recent years have seen vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can used toward this goal. These broadly classified three categories. Deoxygenative functionalizations, representing derivatization C–O bond, enable alcohol act as leaving group formation new C–C bonds. Etherifications, characterized by O–H represent classical reactivity has been modernized include mild reaction conditions, diverse partners, high selectivities. Lastly, chain reactions described, wherein acts mediator formal C–H alkyl backbone. Each these classes transformation will discussed context intermolecular arylation, alkylation, related reactions, illustrating alcohols harnessed

Language: Английский

Citations

34
Recent advances in FeCl3-photocatalyzed organic reactions via hydrogen-atom transfer DOI
Xiaoya Yuan, Congcong Wang, Bing Yu

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(9), P. 109517 - 109517

Published: Jan. 21, 2024

Language: Английский

Citations

32
Metal-catalyzed asymmetric reactions enabled by organic peroxides DOI

Nengbo Zhu,

Huijie Yao,

Xiyu Zhang

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(5), P. 2326 - 2349

Published: Jan. 1, 2024

This review summarizes the advances in metal-catalyzed asymmetric reactions enabled by organic peroxides that have been found to exhibit multifunctionalities, for instance, applied as stoichiometric reactants, reagents, or catalytic amount reagents.

Language: Английский

Citations

18
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

3