Divergent Photosensitizer Controlled Reactions of 4‐Hydroxycoumarins and Unactivated Olefins: Hydroarylation and Subsequent [2+2] Cycloaddition DOI Open Access

Rui Chang,

Yubing Pang,

Juntao Ye

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 26, 2023

Herein, we report a photoinduced approach for hydroarylation of unactivated olefins using 4-hydroxycoumarins as the arylating reagent. Key to success this reaction is conversion nucleophilic into electrophilic carbon radicals via photocatalytic arene oxidation, which not only circumvents polarity-mismatch issue encountered under ionic conditions but also accommodates broad substrate scope and inhibits side reactions that were previously observed. Moreover, divergent reactivity was achieved by changing photocatalyst, enabling subsequent [2+2] cycloaddition deliver cyclobutane-fused pentacyclic products are otherwise challenging access in high yields with diastereoselectivity. Mechanistic studies have elucidated mechanism origin reactivity.

Language: Английский

Room-temperature photosynthesis of propane from CO2 with Cu single atoms on vacancy-rich TiO2 DOI Creative Commons
Yan Shen, Chunjin Ren, Lirong Zheng

et al.

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

Published: Feb. 27, 2023

Photochemical conversion of CO2 into high-value C2+ products is difficult to achieve due the energetic and mechanistic challenges in forming multiple C-C bonds. Herein, an efficient photocatalyst for C3H8 prepared by implanting Cu single atoms on Ti0.91O2 atomically-thin layers. promote formation neighbouring oxygen vacancies (VOs) matrix. These modulate electronic coupling interaction between adjacent Ti form a unique Cu-Ti-VO unit A high electron-based selectivity 64.8% (product-based 32.4%), 86.2% total hydrocarbons 50.2%) are achieved. Theoretical calculations suggest that may stabilize key *CHOCO *CH2OCOCO intermediates reduce their energy levels, tuning both C1-C1 C1-C2 couplings thermodynamically-favourable exothermal processes. Tandem catalysis mechanism potential reaction pathway tentatively proposed formation, involving overall (20e- - 20H+) reduction three molecules at room temperature.

Language: Английский

Citations

203
Reticular framework materials for photocatalytic organic reactions DOI
Ning‐Yu Huang,

Yu‐Tao Zheng,

Di Chen

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(22), P. 7949 - 8004

Published: Jan. 1, 2023

Photocatalytic organic reactions, harvesting solar energy to produce high value-added chemicals, have attracted increasing attention as a sustainable approach address the global crisis and environmental issues. Reticular framework materials, including metal-organic frameworks (MOFs) covalent (COFs), are widely considered promising candidates for photocatalysis owing their crystallinity, tailorable pore environment extensive structural diversity. Although design synthesis of MOFs COFs been intensively developed in last 20 years, applications photocatalytic transformations still preliminary stage, making systematic summary necessary. Thus, this review aims provide comprehensive understanding useful guidelines exploration suitable MOF COF photocatalysts towards appropriate reactions. The commonly used reactions categorized facilitate identification reaction types. From practical viewpoint, fundamentals experimental design, active species, performance evaluation external conditions, discussed detail easy experimentation. Furthermore, latest advances COFs, composites, comprehensively summarized according actual sites, together with discussion structure-property relationship. We believe that study will be helpful researchers novel reticular various synthetic applications.

Language: Английский

Citations

105
Molecular engineering of biomimetic donor-acceptor conjugated microporous polymers with full-spectrum response and an unusual electronic shuttle for enhanced uranium(VI) photoreduction DOI
Fengtao Yu, Shanshan Yu,

Chuangye Li

et al.

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 466, P. 143285 - 143285

Published: May 2, 2023

Language: Английский

Citations

70
Cobaloximes: selective nitrite reduction catalysts for tandem ammonia synthesis DOI
Shu‐Lin Meng, Chen Zhang, Chen Ye

et al.

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(4), P. 1590 - 1596

Published: Jan. 1, 2023

Herein, we demonstrate cobaloximes as a bioinspired molecular platform for exclusive ammonia synthesis via electrocatalytic NO 2 − reduction (eNO RR), which attained 98.5% faradaic efficiency (FE) under close-to-neutral conditions.

Language: Английский

Citations

47
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

39
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

34
Red-Light-Based Effective Photocatalysis of a Photosensitive Covalent Organic Framework Triggered Singlet Oxygen DOI

Kai‐Kai Niu,

Tian‐Xiang Luan,

Jing Cui

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2631 - 2641

Published: Feb. 6, 2024

The direct application of low-energy red light for photochemical transformations is synthetically appealing but practically challenging. Covalent organic frameworks (COFs) exhibit significant potential within this domain, owing to their broad spectrum absorption and prevalence in reactions, despite the fact that these photocatalysts are now mainly focused on using ultraviolet (UV) blue light. In study, an imidazole-linked porphyrin-based COF, PyPor-COF, which exhibits a wide band ranging from 200 700 nm, especially strong 630 expected be applied photocatalytic reactions. PyPor-COF possesses capacity selectively generate singlet oxygen (1O2) with high efficiency, renders it efficient photosensitizer reactions olefin cleavages thioanisole photooxidation under present study demonstrates intriguing prospect photoactive COFs as type II utilization photocatalyses.

Language: Английский

Citations

34
Multi‐Functional Integration of Phosphor, Initiator, and Crosslinker for the Photo‐Polymerization of Flexible Phosphorescent Polymer Gels DOI

Yanyan Cao,

Dan Wang, Yongfeng Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: March 8, 2024

A general approach to constructing room temperature phosphorescence (RTP) materials involves the incorporation of a phosphorescent emitter into rigid host or polymers with high glass transition temperature. However, these often suffer from poor processability and suboptimal mechanical properties, limiting their practical applications. In this work, we developed benzothiadiazole-based dialkene (BTD-HEA), multifunctional remarkable yield intersystem crossing (Φ

Language: Английский

Citations

21
Decoupled Artificial Photosynthesis DOI
Linlin Zhang, Yaobing Wang

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: Feb. 27, 2023

Natural photosynthesis (NP) generates oxygen and carbohydrates from water CO2 utilizing solar energy to nourish lives balance levels. Following nature, artificial (AP), typically, overall or splitting, produces fuels chemicals renewable energy. However, hydrogen evolution reduction is inherently coupled with kinetically sluggish oxidation, lowering efficiencies raising safety concerns. Decoupled systems have thus emerged. In this review, we elaborate how decoupled (DAP) evolves NP AP unveil their distinct photoelectrochemical mechanisms in capture, transduction conversion. Advances of DAP are summarized terms photochemical (PC), (PEC), photovoltaic-electrochemical (PV-EC) catalysis based on material device design. The process emphasized. Challenges perspectives future researches also presented.

Language: Английский

Citations

41
Interfacial Charge Transfer Regulates Photoredox Catalysis DOI Creative Commons
Chen Ye, De-Shan Zhang, Bin Chen

et al.

ACS Central Science, Journal Year: 2024, Volume and Issue: 10(3), P. 529 - 542

Published: Feb. 26, 2024

Photoredox catalytic processes offer the potential for precise chemical reactions using light and materials. The central determinant is identified as interfacial charge transfer, which simultaneously engenders distinctive behavior in overall reaction. An in-depth elucidation of main mechanism highlighting complexity transfer can occur through both diffusive direct models, revealing its sophisticated design complex transformations. fundamental photophysics uncover these comprehensive applications a clue future development. This research contributes to growing body knowledge on photoredox catalysis sets stage further exploration this fascinating area research.

Language: Английский

Citations

12