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

Chemical Design of Metal Complexes for Electrochemical Water Oxidation under Acidic Conditions DOI

Zhen‐Tao Yu

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This article discusses fundamentals of electrochemical water oxidation catalysts based on transition metal complexes under acidic conditions, focusing their design strategies and challenges.

Language: Английский

Citations

2
One-Pot Synthesis of Sulfonamides from Unactivated Acids and Amines via Aromatic Decarboxylative Halosulfonylation DOI

P. Scott Pedersen,

David C. Blakemore,

Gary M. Chinigo

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(39), P. 21189 - 21196

Published: Sept. 20, 2023

The coupling of carboxylic acids and amines to form amide linkages is the most commonly performed reaction in pharmaceutical industry. Herein, we report a new strategy that merges these traditional partners generate sulfonamides, important bioisosteres. This method leverages copper ligand-to-metal charge transfer (LMCT) convert aromatic sulfonyl chlorides, followed by one-pot amination corresponding sulfonamide. process requires no prefunctionalization native acid or amine extends diverse set aryl, heteroaryl, s-rich aliphatic substrates. Further, extend this synthesis (hetero)aryl fluorides, which have found utility as "click" handles chemical probes programmable bifunctional reagents. Finally, demonstrate protocols analogue synthesis.

Language: Английский

Citations

41
Photocatalytic Carboxylate to Sulfinamide Switching Delivers a Divergent Synthesis of Sulfonamides and Sulfonimidamides DOI Creative Commons
Jonathan A. Andrews, Jagadeesh Kalepu,

Christopher F. Palmer

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(39), P. 21623 - 21629

Published: Sept. 22, 2023

sulfinamides, sulfonamides, and sulfonimidamides are in-demand motifs in medicinal chemistry, yet methods for the synthesis of alkyl variants that start from simple, readily available feedstocks scarce. In addition, bespoke syntheses each class molecules usually needed. this report, we detail these three distinct sulfur functional groups, using structurally diverse carboxylic acids as starting materials. The method harnesses radical generation acridine photocatalysts 400 nm light with subsequent addition to sulfinylamine reagents, delivering sulfinamide products. Using N-alkoxy reagent t-BuO-NSO trap provides common intermediates, which can be converted a divergent manner either sulfonamides or sulfonimidamides, by treatment sodium hydroxide, an amine, respectively. reactions scalable, tolerate broad range used diversification complex biologically active compounds.

Language: Английский

Citations

40
Enantioselective decarboxylative alkylation using synergistic photoenzymatic catalysis DOI
Shang‐Zheng Sun, Bryce T. Nicholls, David C. Bain

et al.

Nature Catalysis, Journal Year: 2023, Volume and Issue: 7(1), P. 35 - 42

Published: Dec. 18, 2023

Language: Английский

Citations

36
Translating Planar Heterocycles into Three‐Dimensional Analogs by Photoinduced Hydrocarboxylation** DOI Creative Commons
Myriam Mikhael, Sara N. Alektiar, Charles S. Yeung

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: May 18, 2023

The rapid preparation of complex three-dimensional (3D) heterocyclic scaffolds is a key challenge in modern medicinal chemistry. Despite the increased probability clinical success for small molecule therapeutic candidates with 3D complexity, new drug targets remain dominated by flat molecules due to abundance coupling reactions available their construction. In principle, heteroarene hydrofunctionalization offer an opportunity transform readily accessible planar into more three-dimensionally analogs through introduction single molecular vector. Unfortunately, dearomative limited. Herein, we report strategy enable hydrocarboxylation indoles and related heterocycles. This reaction represents rare example that meets numerous requirements broad implementation discovery. transformation highly chemoselective, scope, operationally simple, amenable high-throughput experimentation (HTE). Accordingly, this process will allow existing libraries heteroaromatic compounds be translated diverse exploration classes medicinally relevant molecules.

Language: Английский

Citations

35
Electrophotocatalytic perfluoroalkylation by LMCT excitation of Ag(II) perfluoroalkyl carboxylates DOI
Brandon M. Campbell, Jesse B. Gordon, Elaine C. Reichert

et al.

Science, Journal Year: 2023, Volume and Issue: 383(6680), P. 279 - 284

Published: Dec. 14, 2023

Molecular Ag(II) complexes are superoxidizing photoredox catalysts capable of generating radicals from redox-reticent substrates. In this work, we exploited the electrophilicity centers in [Ag(bpy)

Language: Английский

Citations

32
Dual Transition Metal Electrocatalysis: Direct Decarboxylative Alkenylation of Aliphatic Carboxylic Acids DOI
Jiaqing Lu, Yan Yao, Liubo Li

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(49), P. 26774 - 26782

Published: Nov. 29, 2023

Direct decarboxylative alkenylation of widely available aliphatic carboxylic acids with vinyl halides for the synthesis alkenes all substitution patterns has been accomplished by means Ce/Ni dual transition metal electrocatalysis. The reactions employ alkyl as limiting reagents and exhibit a broad scope respect to both coupling partners. Notably, simple primary could be readily engaged carbon-centered radical precursors in reaction. This new protocol successfully demonstrated direct modification naturally occurring complex is amenable enantioselective arylacetic acid. Mechanistic studies, including series controlled experiments cyclic voltammetry data, allow us probe key intermediates pathway

Language: Английский

Citations

30
An iron-catalyzed C–S bond-forming reaction of carboxylic acids and hydrocarbons via photo-induced ligand to metal charge transfer DOI

Ao-Men Hu,

Jia‐Lin Tu,

Mengqi Luo

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(19), P. 4764 - 4773

Published: Jan. 1, 2023

A photo-induced iron-catalyzed strategy that facilitates the transformation of carboxylic acids and hydrocarbons into thioethers sulfoxides is herein reported.

Language: Английский

Citations

28
Decarboxylative halogenation of aliphatic carboxylic acids catalyzed by iron salts under visible light DOI
Jiahui Qian, Yu Zhang, Weining Zhao

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(20), P. 2764 - 2767

Published: Jan. 1, 2024

A general method of visible light-induced decarboxylative halogenation aliphatic carboxylic acids catalyzed by iron is developed.

Language: Английский

Citations

14
Photoredox Catalytic Phosphine-Mediated Deoxygenative Hydroacylation of Azobenzenes with Carboxylic Acids DOI
Jingya Yang,

Cunhui Wang,

Bao Huang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(2), P. 498 - 502

Published: Jan. 9, 2024

The convenient and precise preparation of N,N′-diarylhydrazides, especially from readily available raw materials, remains highly challenging. Here, a photoredox catalytic phosphine-mediated deoxygenative hydroacylation azobenzenes with abundant carboxylic acids has been developed. With Ir[dF(CF3)ppy]2(dtbbpy)PF6 as the photocatalyst, reactions proceeded smoothly in presence PPh3 under visible light irradiation, delivering various N,N′-diarylhydrazides up to 92% yields. Mechanistic studies revealed that reaction proceeds via catalysis phosphoranyl-radical-mediated C–O bond cleavage acids.

Language: Английский

Citations

13