scholarly journals Photoredox Catalysis Using Heterogenized Iridium Complexes

Author(s):  
Kelly L. Materna ◽  
Leif Hammarström

Heterogenized photoredox catalysts provide a path to generating chemicals in an environmentally friendly way, with facile reuse of catalysts in batch or continuous processes. In this study, heterogenized iridium complexes as photoredox catalysts were assembled via covalent attachment to three metal oxide surfaces (ITO, ZrO<sub>2</sub>, Al<sub>2</sub>O<sub>3</sub>) either in the form of thin films or nanopowders and tested as photoredox catalysts for reductive dehalogenation of bromoacetophenone to acetophenone. All catalysts produced acetophenone with high conversions and yields. The fastest reactions were complete in fifteen minutes under mild conditions using Al<sub>2</sub>O<sub>3</sub> surfaces, which provided the most robust and reusable supports. The catalytic performance was compared on both nanopowder and thin film supports, showing that both constructs could be used for photoredox catalysis. The nanopowder-based catalysts resulted in faster and more efficient catalysis, while the thin film-immobilized catalysts were more robust and easily reused. Importantly, the thin film constructs show promise for future photoelectrochemical and electrochemical photoredox setups. Finally, all catalysts could be reused 2-3 times, performing at least 1000 turnovers with Al<sub>2</sub>O<sub>3 </sub>supports, highlighting that heterogenized catalysts can perform photoredox catalysis in an environmentally friendly fashion. <br>

2021 ◽  
Author(s):  
Kelly L. Materna ◽  
Leif Hammarström

Heterogenized photoredox catalysts provide a path to generating chemicals in an environmentally friendly way, with facile reuse of catalysts in batch or continuous processes. In this study, heterogenized iridium complexes as photoredox catalysts were assembled via covalent attachment to three metal oxide surfaces (ITO, ZrO<sub>2</sub>, Al<sub>2</sub>O<sub>3</sub>) either in the form of thin films or nanopowders and tested as photoredox catalysts for reductive dehalogenation of bromoacetophenone to acetophenone. All catalysts produced acetophenone with high conversions and yields. The fastest reactions were complete in fifteen minutes under mild conditions using Al<sub>2</sub>O<sub>3</sub> surfaces, which provided the most robust and reusable supports. The catalytic performance was compared on both nanopowder and thin film supports, showing that both constructs could be used for photoredox catalysis. The nanopowder-based catalysts resulted in faster and more efficient catalysis, while the thin film-immobilized catalysts were more robust and easily reused. Importantly, the thin film constructs show promise for future photoelectrochemical and electrochemical photoredox setups. Finally, all catalysts could be reused 2-3 times, performing at least 1000 turnovers with Al<sub>2</sub>O<sub>3 </sub>supports, highlighting that heterogenized catalysts can perform photoredox catalysis in an environmentally friendly fashion. <br>


Synthesis ◽  
2020 ◽  
Author(s):  
Jia-Jia Zhao ◽  
Hong-Hao Zhang ◽  
Shouyun Yu

Visible light photoredox catalysis has recently emerged as a powerful tool for the development of new and valuable chemical transformations under mild conditions. Visible-light promoted enantioselective radical transformations of imines and iminium intermediates provide new opportunities for the asymmetric synthesis of amines and asymmetric β-functionalization of unsaturated carbonyl compounds. In this review, the advance in the catalytic asymmetric radical functionalization of imines, as well as iminium intermediates, are summarized. 1 Introduction 2 The enantioselective radical functionalization of imines 2.1 Asymmetric reduction 2.2 Asymmetric cyclization 2.3 Asymmetric addition 2.4 Asymmetric radical coupling 3 The enantioselective radical functionalization of iminium ions 3.1 Asymmetric radical alkylation 3.2 Asymmetric radical acylation 4 Conclusion


2021 ◽  
pp. 174751982110325
Author(s):  
Yan Xiao ◽  
Jiyu Gao ◽  
Peng Chen ◽  
Guangliang Chen ◽  
Zicheng Li ◽  
...  

A series of symmetrical 1,4-disubstituted buta-1,3-diynes is prepared with excellent yields (up to 95%) through homocoupling of terminal alkynes catalyzed by a copper salt under solvent-free conditions. This method provides an environmentally friendly process to prepare 1,3-diynes in short reaction times under mild conditions. Furthermore, the method is suitable for a wide substrate scope and has excellent functional group compatibility. The reaction can also be scaled up to gram level.


Molecules ◽  
2020 ◽  
Vol 25 (22) ◽  
pp. 5270
Author(s):  
Zhenbo Yuan ◽  
Xuanzhong Liu ◽  
Changmei Liu ◽  
Yan Zhang ◽  
Yijian Rao

Non-proteinogenic amino acids have attracted tremendous interest for their essential applications in the realm of biology and chemistry. Recently, rising C–H functionalization has been considered an alternative powerful method for the direct synthesis of non-proteinogenic amino acids. Meanwhile, photochemistry has become popular for its predominant advantages of mild conditions and conservation of energy. Therefore, C–H functionalization and photochemistry have been merged to synthesize diverse non-proteinogenic amino acids in a mild and environmentally friendly way. In this review, the recent developments in the photo-mediated C–H functionalization of proteinogenic amino acids derivatives for the rapid synthesis of versatile non-proteinogenic amino acids are presented. Moreover, postulated mechanisms are also described wherever needed.


2021 ◽  
Author(s):  
Filip Jones Benjamin Moses ◽  
Gcina Mamba ◽  
Sajid A Ansari ◽  
Maruthamani D. ◽  
Muthuraj Velluchamy ◽  
...  

Utilization of environmentally friendly and effective synthesis methods to fabricate visible light responsive photocatalyst with impressive catalytic performance is desirable in photocatalytic water treatment. Herein, we employed the powerful and...


Molecules ◽  
2018 ◽  
Vol 23 (9) ◽  
pp. 2358 ◽  
Author(s):  
David Lopez-Tejedor ◽  
Blanca de las Rivas ◽  
Jose M. Palomo

A novel heterogeneous enzyme-palladium (Pd) (0) nanoparticles (PdNPs) bionanohybrid has been synthesized by an efficient, green, and straightforward methodology. A designed Geobacillus thermocatenulatus lipase (GTL) variant genetically and then chemically modified by the introduction of a tailor-made cysteine-containing complementary peptide- was used as the stabilizing and reducing agent for the in situ formation of ultra-small PdNPs nanoparticles embedded on the protein structure. This bionanohybrid was an excellent catalyst in the synthesis of trans-ethyl cinnamate by Heck reaction at 65 °C. It showed the best catalytic performance in dimethylformamide (DMF) containing 10–25% of water as a solvent but was also able to catalyze the reaction in pure DMF or with a higher amount of water as co-solvent. The recyclability and stability were excellent, maintaining more than 90% of catalytic activity after five cycles of use.


2018 ◽  
Vol 42 (8) ◽  
pp. 419-423
Author(s):  
Li-Jie Zhang ◽  
Xian Yao ◽  
Ying-xin Sun ◽  
Jia-wei Zhang ◽  
Chun Cai

Pd–Ni bimetallic nanoparticles (BMNPs) supported on ZrO2 were prepared by an impregnation–reduction method. The BMNPs showed excellent catalytic performance in Suzuki carbon–carbon cross-coupling reactions and almost quantitative conversion of the substrates was obtained under mild conditions in the absence of ligand. The excellent catalytic performance of the bimetallic catalyst could be a result of the synergistic effect between the two metal components. The catalyst showed outstanding recyclability during the reaction process; no obvious decrease in catalytic performance was observed after five cycles.


2019 ◽  
Vol 55 (30) ◽  
pp. 4383-4386 ◽  
Author(s):  
Rui Xu ◽  
Chun Cai

The first difluoroalkylation–thiolation of alkenes catalyzed by iron-facilitated photoredox has been developed with a broad substrate scope under mild conditions.


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