Metal–organic frameworks for organic transformations by photocatalysis and photothermal catalysis

Chemical Society Reviews, Год журнала: 2024, Номер 53(18), С. 9378 - 9418

Опубликована: Янв. 1, 2024

Organic transformation by light-driven catalysis, especially, photocatalysis and photothermal denoted as photo(thermal) is an efficient, green, economical route to produce value-added compounds. In recent years, owing their diverse structure types, tunable pore sizes, abundant active sites, metal-organic framework (MOF)-based catalysis has attracted broad interest in organic transformations. this review, we provide a comprehensive systematic overview of MOF-based for First, the general mechanisms, unique advantages, strategies improve performance MOFs are discussed. Then, outstanding examples transformations over introduced according reaction type. addition, several representative advanced characterization techniques used revealing charge kinetics intermediates presented. Finally, prospects challenges field proposed. This review aims inspire rational design development materials with improved catalysis.

Язык: Английский

---

An Integrated Carbon Nitride‐Nickel Photocatalyst for the Amination of Aryl Halides Using Sodium Azide

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(24)

Опубликована: Март 25, 2022

The synthesis of primary anilines via sustainable methods remains a challenge in organic synthesis. We report photocatalytic protocol for the selective cross-coupling wide range aryl/heteroaryl halides with sodium azide using photocatalyst powder consisting nickel(II) deposited on mesoporous carbon nitride (Ni-mpg-CN

Язык: Английский

---

Electrophilic Aminating Agents in Total Synthesis

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(49), С. 25640 - 25666

Опубликована: Май 4, 2021

Classical amination methods involve the reaction of a nitrogen nucleophile with an electrophilic carbon center; however, in recent years, umpoled strategies have gained traction where source acts as electrophile. A wide range aminating agents are now available, and these underpin powerful C-N bond-forming processes. In this Review, we highlight strategic use total synthesis.

Язык: Английский

---

Recent advances in visible light-induced C(sp3)–N bond formation

Nature Reviews Chemistry, Год журнала: 2022, Номер 6(8), С. 544 - 561

Опубликована: Июль 11, 2022

Язык: Английский

---

Light-Induced Activation of C–X Bond via Carbonate-Assisted Anion−π Interactions: Applications to C–P and C–B Bond Formation

Organic Letters, Год журнала: 2023, Номер 25(6), С. 923 - 927

Опубликована: Фев. 8, 2023

We have presented a carbonate anion assisted photochemical protocol for the C-X bond activation. Anion-π interactions been leveraged to generate aryl radicals from easily accessible halides that are further utilized in C-P and C-B formation reactions with excellent reactivity broad functional group tolerance. Spectroscopic investigations DFT studies were conducted mechanistic insights. This inexpensive method alleviates use of photocatalyst need preactivation substrate light-induced activation bonds.

Язык: Английский

---

Generation and Application of Aryl Radicals Under Photoinduced Conditions

Chemistry - A European Journal, Год журнала: 2024, Номер 30(31)

Опубликована: Март 28, 2024

Abstract Photoinduced aryl radical generation is a powerful strategy in organic synthesis that facilitates the formation of diverse carbon‐carbon and carbon‐heteroatom bonds. The synthetic applications photoinduced complex compounds, including natural products, physiologically significant molecules, functional materials, have received immense attention. An overview current developments production methods their uses given this article. A generalized idea how to choose reagents approach for radicals described, along with techniques associated mechanistic insights. Overall, article offers critical assessment results as well selection reaction parameters specific context cascades, cross‐coupling reactions, functionalization, selective C−H functionalization substrates.

Язык: Английский

---

Recent advances in C(sp³)–N bond formation via metallaphoto-redox catalysis

Chemical Communications, Год журнала: 2024, Номер 60(50), С. 6340 - 6361

Опубликована: Янв. 1, 2024

In this review, the state-of-the-art advances in radical-involved C(sp 3 )–N bond formation via metallaphotoredox catalysis have been highlighted, which are organized according to different catalytic modes, reaction types, and substrate classes.

Язык: Английский

---

Hydrogen‐Bond‐Mediated Formation of C−N or C=N Bond during Photocatalytic Reductive Coupling Reaction over CdS Nanosheets

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(26)

Опубликована: Апрель 19, 2024

Abstract Reductive amination of carbonyl compounds and nitro represents a straightforward way to attain imines or secondary amines, but it is difficult control the product selectivity. Herein, we report selective formation C−N C=N bond readily manipulated through solvent‐induced hydrogen bridge, facilitating swift photocatalytic reductive coupling process. The reductive‐coupling with using formic acid sodium formate as donors over CdS nanosheets selectively generates bonds in acetonitrile solvent; while taking methanol solvent, are hydrogenated via hydrogen‐bonding activation. Experimental theoretical study reveals that building hydrogen‐bond bridge between hydroxyl groups N atoms motifs facilitates transfer from surface upon illumination, resulting rapid hydrogenation give rise amines bonds. Our method provides simple selectivity by altering solvents organic transformations.

Язык: Английский

---

Photoinduced ligand to metal charge transfer enabling cerium mediated decarboxylative alkylation of quinoxalin-2(1H)-ones

Chemical Communications, Год журнала: 2022, Номер 58(23), С. 3831 - 3834

Опубликована: Янв. 1, 2022

Here, we report the cerium-mediated decarboxylative alkylation of quinoxalin-2(1H)-ones utilizing feedstock carboxylic acids as a radical precursor via photoinduced-LMCT. This operationally simple protocol overcomes limitation direct use to access alkyl radicals. Spectroscopic investigations reveal photoinduced LMCT and CO2 evolving events. We have utilized broad range (1° 3° acids), amino pharmaceutically-important coupling partner synthesise desired alkylated heterocyclic product in good excellent yields.

Язык: Английский

---

Blue Light Irradiated Metal-, Oxidant-, and Base-Free Cross-Dehydrogenative Coupling of C(sp²)–H and N–H Bonds: Amination of Naphthoquinones with Amines

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(11), С. 7401 - 7424

Опубликована: Май 12, 2023

Herein, we report a blue-light-driven amination of C(sp2)-H bond naphthoquinones and quinones with the N-H primary secondary amines for synthesis 2-amino-naphthoquinones 2-amino-quinones. The coupling wide array aliphatic, aromatic, chiral, primary, having electron donating (-CH3, -OCH3, -SCH3), withdrawing (-F, -Cl, -Br, -I), CO2H, -OH, -NH2 groups acidic protons selectively occurred to afford C-N coupled in 60-99% yields hydrogen gas as byproduct methanol solvent without using any additional reagents, additives, oxidant under blue light irradiation. Mechanistic insight by DFT computation, controlled experiments, kinetic isotopic effect, substitution effect substrates suggest that reaction proceeds radical pathway which naphthoquinone forms highly oxidizing naphthoquinonyl biradical upon irradiation (457 nm). Consequently, transfer from electron-rich amine an leads anion aminyl cation, followed proton delocalization leading carbon-centered radical. cross-coupling nitrogen radicals bond, subsequent elimination (which was also confirmed GC-TCD), affording 2-amino-1,4-naphthoquinone metal-, reagent-, base-, oxidant-free conditions.

Язык: Английский

---