CH-Activation reactions of nitroarenes: current status and outlook

Author(s):  
Saumitra Sengupta ◽  
Parthasarathi Das

Ring substitution reactions of nitroarenes remain an under-developed area of organic synthesis, confined to narrow domains of SNAr and SNArH reactions. Searching for alternate methodologies, we took stock of CH-activation...


2020 ◽  
Author(s):  
Shogo Mori ◽  
Takahiro Aoki ◽  
Kaliyamoorthy Selvam ◽  
Shunichi Fukuzumi ◽  
Jieun Jung ◽  
...  

Despite the continuing popularity of radical reactions in organic synthesis, much remains to be explored in this area. Herein, we describe how spatiotemporal control can be exerted over the formation and reactivity of divergent exchangeable formamide radicals using nickel complexes with a semiconductor material (TiO<sub>2</sub>) under irradiation from near-UV–Vis light. Depending on the bipyridine ligand used and the quantity of the nickel complex that is hybridized on or nonhydridized over the TiO<sub>2</sub> surface, these radicals selectively undergo substitution reactions at the carbon center of carbon–bromine bonds that proceed via three different pathways. As the scalable production of formamides from CO<sub>2</sub> does not produce salt waste, these methods could add a new dimension to the search for carbon neutrality through the indirect incorporation of CO<sub>2</sub> into organic frameworks.



2021 ◽  
Vol 25 ◽  
Author(s):  
Kevin George ◽  
Sathananthan Kannadasan

: Toluene and its derivatives became well established as versatile scaffolds in organic synthesis over the last few decades. This review provides a brief and concise overview of the current status and latest methodologies in the synthetic utility of toluene and its derivatives by exploiting both the alkyl-sp3 and aryl-sp2 carbons via C-H activation. The review also explores the effect of various substituents on the toluene derivatives in facilitating different reactions.



2021 ◽  
Vol 15 (1) ◽  
pp. 71-81
Author(s):  
Ashish Bhatt ◽  
Darshankumar Prajapati ◽  
Akshaya Gupte

Nitriles are organic compounds consisting of −C≡N group. They are frequently known to occur in nature and as intermediate by-products and waste products of various chemical, pharmaceutical, and agricultural industries. They are also found in fruit pits, cabbage, cauliflower, and sprouts, which are released upon hydrolysis. Nitrile converting enzymes like nitrilases have been extracted from microorganisms and plants. Nitrilase-mediated biocatalysis reactions have continuously aroused widespread interest to scientists and entrepreneurs in organic synthesis. Nitrile converting biocatalysts (Nitrilases) are now of substantial industrial interest from the perspective of treating toxic nitrile and cyanide-containing compounds. Nitrile degrading enzymes generally consist of nitrilases and amidases. The aim of the current review is to summarize the recent advancements on regioselective nitrilases concerning their fundamental researches and their application in the synthesis of series of high-value fine chemicals and pharmaceuticals. The present review also focuses on the utility of nitrile converting enzyme, sources, properties, classification, structure, and applications as well.



Science ◽  
2020 ◽  
Vol 367 (6477) ◽  
pp. 559-564 ◽  
Author(s):  
Haohua Huo ◽  
Bradley J. Gorsline ◽  
Gregory C. Fu

Stereochemical control in the construction of carbon-carbon bonds between an alkyl electrophile and an alkyl nucleophile is a persistent challenge in organic synthesis. Classical substitution reactions via SN1 and SN2 pathways are limited in their ability to generate carbon-carbon bonds (inadequate scope, due to side reactions such as rearrangements and eliminations) and to control stereochemistry when beginning with readily available racemic starting materials (racemic products). Here, we report a chiral nickel catalyst that couples racemic electrophiles (propargylic halides) with racemic nucleophiles (β-zincated amides) to form carbon-carbon bonds in doubly stereoconvergent processes, affording a single stereoisomer of the product from two stereochemical mixtures of reactants.



2020 ◽  
Author(s):  
Shogo Mori ◽  
Takahiro Aoki ◽  
Kaliyamoorthy Selvam ◽  
Shunichi Fukuzumi ◽  
Jieun Jung ◽  
...  

Despite the continuing popularity of radical reactions in organic synthesis, much remains to be explored in this area. Herein, we describe how spatiotemporal control can be exerted over the formation and reactivity of divergent exchangeable formamide radicals using nickel complexes with a semiconductor material (TiO<sub>2</sub>) under irradiation from near-UV–Vis light. Depending on the bipyridine ligand used and the quantity of the nickel complex that is hybridized on or nonhydridized over the TiO<sub>2</sub> surface, these radicals selectively undergo substitution reactions at the carbon center of carbon–bromine bonds that proceed via three different pathways. As the scalable production of formamides from CO<sub>2</sub> does not produce salt waste, these methods could add a new dimension to the search for carbon neutrality through the indirect incorporation of CO<sub>2</sub> into organic frameworks.



Tetrahedron ◽  
2005 ◽  
Vol 61 (40) ◽  
pp. 9533-9540 ◽  
Author(s):  
Vijay Nair ◽  
Siji Thomas ◽  
Smitha C. Mathew ◽  
N. Vidya ◽  
Nigam P. Rath


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