Palladium-(Acyclic Diaminocarbene) Species as Alternative to Palladium-(Nitrogen Heterocyclic Carbenes) in Cross-Coupling Catalysis

Author(s):  
Vadim P. Boyarskiy ◽  
Konstantin V. Luzyanin ◽  
Vadim Yu. Kukushkin
2020 ◽  
Vol 09 ◽  
Author(s):  
Minita Ojha ◽  
R. K. Bansal

Background: During the last two decades, horizon of research in the field of Nitrogen Heterocyclic Carbenes (NHC) has widened remarkably. NHCs have emerged as ubiquitous species having applications in a broad range of fields, including organocatalysis and organometallic chemistry. The NHC-induced non-asymmetric catalysis has turned out to be a really fruitful area of research in recent years. Methods: By manipulating structural features and selecting appropriate substituent groups, it has been possible to control the kinetic and thermodynamic stability of a wide range of NHCs, which can be tolerant to a variety of functional groups and can be used under mild conditions. NHCs are produced by different methods, such as deprotonation of Nalkylhetrocyclic salt, transmetallation, decarboxylation and electrochemical reduction. Results: The NHCs have been used successfully as catalysts for a wide range of reactions making a large number of building blocks and other useful compounds accessible. Some of these reactions are: benzoin condensation, Stetter reaction, Michael reaction, esterification, activation of esters, activation of isocyanides, polymerization, different cycloaddition reactions, isomerization, etc. The present review includes all these examples published during the last 10 years, i.e. from 2010 till date. Conclusion: The NHCs have emerged as versatile and powerful organocatalysts in synthetic organic chemistry. They provide the synthetic strategy which does not burden the environment with metal pollutants and thus fit in the Green Chemistry.


Catalysts ◽  
2018 ◽  
Vol 8 (4) ◽  
pp. 141 ◽  
Author(s):  
Vladimir Mikhaylov ◽  
Viktor Sorokoumov ◽  
Denis Liakhov ◽  
Alexander Tskhovrebov ◽  
Irina Balova

Two types of immobilized on the amino-functionalized polystyrene-supported acyclic diaminocarbene palladium complexes (ADC-PdII) are investigated under Sonogashira cross-coupling conditions. Depending on substituents in the diaminocarbene fragment immobilized ADC-PdII, systems are found to have different catalytic activity and stability regarding Pd-leaching. PdII-diaminocarbenes possessing protons at both nitrogen atoms smoothly decompose into Pd0-containing species providing a catalytic “cocktail system” with high activity and ability to reuse within nine runs. Polymer-supported palladium (II) complex bearing NBn–Ccarbene–NH-moiety exhibits greater stability while noticeably lower activity under Sonogashira cross-coupling. Four molecular ADC-PdII complexes are also synthesized and investigated with the aim of confirming proposed base-promoted pathway of ADC-PdII conversion through carbodiimide into an active Pd0 forms.


2020 ◽  
Vol 504 ◽  
pp. 119446
Author(s):  
Suryakant Nagar ◽  
Sucheta Chatterjee ◽  
Dibakar Goswami ◽  
David B. Cordes ◽  
A.M.Z. Slawin ◽  
...  

2020 ◽  
Author(s):  
Yumiao Ma

The formal oxygen atom transfer (OAT) reaction with nitrogen heterocyclic carbenes (NHCs) as oxygen atom acceptor was designed and studied by density functional theory (DFT) calculations. Several properly designed NHCs were predicted to exhibit high reactivity towards the formal OAT reaction with aldehydes, in the presence of an intramolecular phosphine motif, which provides a new method to generate phosphorus ylide from aldehydes. Furthermore, the OAT reaction of NHCs with carbon dioxide (CO<sub>2</sub>) was predicted to occur at room temperature to release carbon monoxide, aided by an intramolecular nucleophile. These results may give insights about new methodologies for ylide preparation and CO<sub>2</sub> reduction.


2018 ◽  
Vol 20 (29) ◽  
pp. 19552-19559 ◽  
Author(s):  
M. Merced Montero-Campillo ◽  
Ibon Alkorta ◽  
José Elguero

Carbon disulfide (CS2) and carbonyl sulfide (OCS) are indirect greenhouse gases that can be effectively trapped by classical, abnormal and remote nitrogen heterocyclic carbenes (NHCs), according to high levelab initiocalculations.


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