Titanium in photocatalytic organic transformations: current applications and future developments

Tu, Jia-Lin; Huang, Binbin

doi:10.1039/d4ob01152j

Org. Biomol. Chem.

2024

DOI: 10.1039/d4ob01152j

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Titanium in photocatalytic organic transformations: current applications and future developments

Jia-Lin Tu,

Binbin Huang

Abstract: Titanium, as an important transition-metal, has garnered extensive attention in both industry and academia due to its excellent mechanical properties, corrosion resistance, and unique reactivity in organic synthesis. In the...

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Cited by 9 publications

References 247 publications

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Light‐Induced Direct Decarboxylative Functionalization of Aromatic Carboxylic Acids

Tu,

Shen,

Huang

2024

Adv Synth Catal

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Aryl radicals are important intermediates in organic synthesis. The generation of these reactive species via direct decarboxylation of inexpensive and readily available aromatic carboxylic acids is an attractive goal. However, such a process intrinsically exhibits high energy barriers to overcome, which in consequence usually require precious metal catalysis, stoichiometric oxidants and harsh conditions, suffering from limitations such as poor functional group tolerance and low atom economy. In recent years, visible‐light‐induced photochemical reactions have provided new approaches to address this challenge. Three major strategies have been introduced in this emerging field: 1) one‐pot in‐situ activation of benzoic acids to generate intermediates such as benzoyl hypobromites or hypoiodites; 2) the use of specialized photocatalysts like biphenyl/1,4‐dicyanobenzene to promote decarboxylation through photo‐induced electron transfer or charge transfer processes; 3) photo‐induced LMCT (Ligand‐to‐Metal Charge Transfer) strategy where copper or iron salts coordinate to the carboxylate anion and generate aromatic radicals upon visible light excitation. On the basis of these three strategies, this review will systematically summarize the development of visible‐light‐induced direct decarboxylative functionalization of aromatic carboxylic acids, focusing on the reaction mechanism and substrate scope, and discuss their prospects in organic synthesis.

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Light‐Induced Direct Decarboxylative Functionalization of Aromatic Carboxylic Acids

Tu,

Shen,

Huang

2024

Adv Synth Catal

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Catalytic Construction of C(sp³)−Ge Bonds: Recent Advances and Future Perspectives

Tu,

Huang

2024

Adv Synth Catal

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Germanium (Ge), a congener of carbon, possesses unique properties that hold extensive potential for applications across multiple domains. Recent years have seen significant progress in the development of carbon‐germanium bond formation strategies, particularly those for more challenging C(sp3)‐Ge bonds. This review systematically summarizes the recent advances in C(sp3)‐Ge bond forming methodologies, with particular emphasis on (1) the versatility of transition‐metals, including iron, nickel, copper, rhodium and palladium, as catalysts in broadening reaction scope and controlling selectivity; (2) the powerfulness of organic photocatalysis in achieving mild and selective bond formation, and (3) the sustainability of catalytic electrosynthesis in facilitating chemical oxidant‐/reductant‐free conversions. Additionally, examples of (4) non‐catalytic strategies are also discussed. The representative scopes, as well as mechanistic proposals, of these protocols are highlighted. Through an overview on the current state of research, this review aims to offer insights into the catalytic construction of C(sp3)‐Ge bonds, and provide perspectives on future research directions to address the current challenges.

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Chromium in Visible‐Light Photocatalysis: Unique Reactivity, Mechanisms and Future Directions

Shen,

2024

Eur J Org Chem

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Visible‐light photocatalysis has emerged as a prominent research area in modern organic synthesis and environmental science. As an important transition metal, chromium has garnered widespread attention in the field of visible‐light photocatalysis in recent years, primarily manifested in the following aspects: a) the unique photochemical properties of chromium(III) complexes endow them with longer excited‐state lifetimes and higher reactivities; b) by harnessing visible light to induce single‐electron transfer or hydrogen atom transfer to generate radicals, which subsequently form alkyl‐chromium(III) intermediates with chromium(II) ligands, these intermediates can selectively attack electron‐deficient carbonyl compounds, enabling the construction of target products; c) following metals like cerium, copper, iron, nickel, cobalt, titanium, and bismuth, the ligand‐to‐metal charge transfer (LMCT) reaction pathways in chromium photocatalysis have also been extensively investigated.This review will provide a comprehensive summary of recent research on chromium‐mediated photocatalytic reactions, offering an in‐depth exploration of their unique reactivity, mechanisms, and future directions.

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Titanium in photocatalytic organic transformations: current applications and future developments

Abstract: Titanium, as an important transition-metal, has garnered extensive attention in both industry and academia due to its excellent mechanical properties, corrosion resistance, and unique reactivity in organic synthesis. In the...

Cited by 9 publications

References 247 publications

Light‐Induced Direct Decarboxylative Functionalization of Aromatic Carboxylic Acids

Light‐Induced Direct Decarboxylative Functionalization of Aromatic Carboxylic Acids

Catalytic Construction of C(sp³)−Ge Bonds: Recent Advances and Future Perspectives

Chromium in Visible‐Light Photocatalysis: Unique Reactivity, Mechanisms and Future Directions

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Titanium in photocatalytic organic transformations: current applications and future developments

Abstract: Titanium, as an important transition-metal, has garnered extensive attention in both industry and academia due to its excellent mechanical properties, corrosion resistance, and unique reactivity in organic synthesis. In the...

Cited by 9 publications

References 247 publications

Light‐Induced Direct Decarboxylative Functionalization of Aromatic Carboxylic Acids

Light‐Induced Direct Decarboxylative Functionalization of Aromatic Carboxylic Acids

Catalytic Construction of C(sp3)−Ge Bonds: Recent Advances and Future Perspectives

Chromium in Visible‐Light Photocatalysis: Unique Reactivity, Mechanisms and Future Directions

Contact Info

Product

Resources

About

Catalytic Construction of C(sp³)−Ge Bonds: Recent Advances and Future Perspectives