Keto-enol tautomerism as transformative electron/hole traps to promote charge carrier separation for record-high H2O2 photosynthesis in real world DOI Creative Commons
Tianyi Ma, Fang Ma, Xiaodong Sun

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 30, 2024

Abstract Covalent organic frameworks (COFs) are excellent photocatalysts for hydrogen peroxide (H2O2) photosynthesis, but often limited by retarded charge carrier separation. Presently, donor-acceptor (D-A) type COFs commonly used to enhance the separation of photogenerated electrons and holes at molecular level promoting migration towards acceptor movement donor. However, significantly slower kinetics synchronous water oxidation oxygen reduction reactions (WOR ORR) result in accumulation carriers, which induces strong Coulomb forces, turn adversely affecting efficiency D-A COFs. Herein, it is observed that keto-enol tautomerism can function as dynamic traps both holes, alternately capturing them, while counterpart participate consumed during asynchronous reactions. This represents first example T-C (T denotes units; C catalytic active units), effectively weaken force reducing accumulation, resulting rapid transfer prolonged lifetimes free carriers efficient alternating photocatalytic WOR ORR. Our in-depth research indicates imine based on 2,4,6-trihydroxybenzaldehyde-1,3,5-tricarbaldehyde (Tp series) exhibit enhanced activity compared those 1,3,5-benzenetricarboxaldehyde (BT series), be attributed occurrence tautomerization. Notably, optimal Tp COF (TpBpy) displays an ultrafast rate H2O2 reaching 3.79 mM h-1, surpassing all previously reported photocatalysts. More importantly, when employed a flow-reactor system, TpBpy also showcases exceptional effectiveness continuous synthesis, achieving solar-to-chemical conversion (SCC) 0.038%, representing highest performance recorded date under natural sunlight conditions. work offers molecular-level guidance designing photosynthesis proposes standardized criteria obtaining reliable SCC values.

Language: Английский

Design and Preparation of Heterostructured Cu2O/TiO2 Materials for Photocatalytic Applications DOI Creative Commons

Yating Tai,

Boxuan Yang, Jing Li

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(21), P. 5028 - 5028

Published: Oct. 24, 2024

The extensive use of fossil fuels has sped up the global development world economy and is accompanied by significant problems, such as energy shortages environmental pollution. Solar energy, an inexhaustible clean resource, emerged a promising sustainable alternative. Light irradiation can be transformed into electrical/chemical which used to remove pollutants or transform contaminants high-value-added chemicals through photocatalytic reactions. Therefore, photocatalysis strategy overcome increasing problems. As well-known, photocatalysts are key components systems. Among widely investigated photocatalysts, titanium dioxide (TiO

Language: Английский

Citations

8
A green Heck reaction protocol towards trisubstituted alkenes, versatile pharmaceutical intermediates DOI Creative Commons
Giacomo Rossino, Giorgio Marrubini, Margherita Brindisi

et al.

Frontiers in Chemistry, Journal Year: 2024, Volume and Issue: 12

Published: July 10, 2024

The Heck reaction is widely employed to build a variety of biologically relevant scaffolds and has been successfully implemented in the production active pharmaceutical ingredients (APIs). Typically, with terminal alkenes gives high yields stereoselectivity toward

Language: Английский

Citations

3
Divergent Synthesis of Chiroptical Molecular Switches Based on 1,2-Diaxial Atropisomers DOI Creative Commons

Tian‐Jiao Han,

Qingxiang Yang, Jin‐Feng Hu

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(11), P. 4445 - 4454

Published: Oct. 14, 2024

The development of chiroptical molecular switches for chiral sensing, data communication, optical displays, logic gates, and asymmetric catalysis is currently a vibrant frontier science technology. Herein, we report practical artificial dynamic system based on 1,2-diaxial atropisomer. Organocatalytic parallel kinetic resolution allows the divergent synthesis two sets stereoisomers with vicinal C-C N-N axes from same racemic single-axis substrates. By simply varying configuration single catalyst, all four are accessible. successive conduction covalent unlocking/locking thermal-isomerization processes enables sequential switching between atropisomeric states electronic circular dichroism signal reversal, providing an example multistate switches.

Language: Английский

Citations

3
Ni‐SPO‐Al Catalyzed Stereoselective C–H Alkenylation of Quinazolinones with Alkynes to Prepare trans‐Isomers DOI
Yaqi Zhang,

Qiang Ni,

Rihui Cao

et al.

European Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 28(5)

Published: Jan. 4, 2025

Abstract A stereoselective Ni−Al bimetal‐catalyzed C−H alkenylation of quinazolinones with alkynes has been successfully developed. Good selectivity Z‐type quinazolinone products was obtained using readily available substrates, which exhibits a trans‐configuration opposite to the conventional alkynylation reactions and improves diversity compounds. In addition, reaction process further explored through KIE other control experiments, possible mechanism proposed.

Language: Английский

Citations

0
Palladium-Catalyzed Divergent Synthesis from o-Sulfonamido Trifluoroacetophenones and 2-En-4-ynyl Carbonates DOI

Meng-Qi Gan,

Jian‐Xiang Zhu,

Zhichao Chen

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 15, 2025

Here we present a palladium-catalyzed divergent transformative reaction between o-sulfonamido trifluoroacetophenones and 2-en-4-ynyl carbonates. A spectrum of enantioenriched 2,5-dihydrofuran-fused tetrahydroquinolines bearing either (Z)- or (E)-exocyclic double bond are constructed with moderate to high enantioselectivity from 5-aryl-substituted carbonates by tuning palladium sources, while analogous 2,3-dihydrofuran-fused products furnished using 5-alkyl-substituted ones.

Language: Английский

Citations

0
Stereodivergent Construction of Enamides via a Radical-Mediated Isodesmic Reaction DOI
Yingying Xu, Xin Zhang, X. Kang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6749 - 6759

Published: April 10, 2025

Language: Английский

Citations

0
Photocatalyzed E → Z contra-thermodynamic isomerization of enamides DOI

Wenhui Ma,

Guanhua Ding,

Zenghui Ye

et al.

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

We reported an efficient photocatalytic activation of ( E )-enamides via energy transfer by excited Ir(ppy) 3 , enabling selective Z )-enamide synthesis under mild conditions with high efficiency (S/C up to 10 000).

Language: Английский

Citations

0
Asymmetric Olefin Isomerization via Phase-Transfer-Catalyzed [1,3]-Hydrogen Transfer for Access to Axially Chiral Furan-Benzimidazoles DOI

Yu‐Qing Guan,

Kaili Ma, Dong‐Chao Wang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 9, 2025

An efficient catalytic asymmetric olefin isomerization of axially chiral methylene dihydrofuran-benzimidazoles via kinetic resolution is reported. Under mild phase-transfer catalysis, furan-benzimidazole compounds and recovered were obtained in high ee. The combination the TBD-catalyzed provided access to both enantiomers furan-benzimidazoles. Deuterium-labeling experiments reveal intramolecular [1,3]-H transfer mechanism. utility this method was demonstrated by scale-up synthesis functionalization products.

Language: Английский

Citations

0
Iridium-Catalyzed Asymmetric Allylic Substitution with Sequential Boron Incorporation DOI

Wan-Yi Xu,

Lihong Zhang, Le Wang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 9, 2025

An iridium-catalyzed asymmetric allylic substitution with sequential boron incorporation is reported. The reaction accommodates a wide range of substrates, affording chiral N,O-bidentate difluoroboron complexes in excellent yields high enantioselectivities. Furthermore, decigram-scale reaction, synthetic transformations, as well photophysical property investigations the are explored.

Language: Английский

Citations

0
Enantiospecific 1,3-hydrogen transfer of alkenes and alkynes DOI
Qi Liu,

Wan-Yi Xu,

Cen-Cen You

et al.

Trends in Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 1, 2024

Language: Английский

Citations

3