Ni(COD)(DMFU): A Heteroleptic 16-Electron Precatalyst for 1,2-Diarylation of Alkenes

Synlett ◽  
2021 ◽  
Author(s):  
Nana Kim ◽  
Van T. Tran ◽  
Omar Apolinar ◽  
Steven Wisniewski ◽  
Martin Eastgate ◽  
...  

Electron-deficient olefin (EDO) ligands are known to promote a variety of nickel-catalyzed cross-coupling reactions, presumably by accelerating the reductive elimination step and preventing undesired β-hydride elimination. While there is a growing body of experimental and computational evidence elucidating the beneficial effects of EDO ligands, significant gaps remain in our understanding of the underlying coordination chemistry of the Ni–EDO species involved. In particular, most procedures rely on in situ assembly of the active catalyst, and there is a paucity of pre-ligated Ni-EDO precatalysts. Herein, we investigate the 16-electron, heteroleptic nickel complex, Ni(COD)(DMFU), and examine the performance of this complex as a precatalyst in 1,2-diarylation of alkenes.

2019 ◽  
Author(s):  
Randolph Escobar ◽  
Jeffrey Johannes

<div>While carbon-heteroatom cross coupling reactions have been extensively studied, many methods are specific and</div><div>limited to a set of substrates or functional groups. Reported here is a method that allows for C-O, C-N and C-S cross coupling reactions under one general methodology. We propose that an energy transfer pathway, in which an iridium photosensitizer produces an excited nickel (II) complex, is responsible for the key reductive elimination step that couples aryl halides to 1° and 2° alcohols, anilines, thiophenols, carbamates and sulfonamides.</div>


2010 ◽  
Vol 12 (8) ◽  
pp. 1834-1841 ◽  
Author(s):  
Yugang Cui ◽  
Ilaria Biondi ◽  
Manish Chaubey ◽  
Xue Yang ◽  
Zhaofu Fei ◽  
...  

ChemInform ◽  
2014 ◽  
Vol 45 (28) ◽  
pp. no-no
Author(s):  
Mojtaba Amini ◽  
Abbas Tarassoli ◽  
Saeed Yousefi ◽  
Sepideh Delsouz-Hafshejani ◽  
Mina Bigdeli ◽  
...  

2019 ◽  
Author(s):  
Dengmengfei Xiao ◽  
Lili Zhao ◽  
Diego Andrada

Unstrained cyclic ketones can participate in cooperative Suzuki-Miyaura cross-coupling type reaction using rhodium(I)-based catalyst via C-C bond activation. The regioselectivity indicates a trend where the most substituted side is activated and it is controlled by the beta-substituents. In this work, Density Functional Theory (DFT) calculations have been carried out to disclose the underlying mechanism in the reaction of a ketone series and arylboronate using ylidene as ancillary ligand and pyridine as co-catalysts. The computed energies suggest the reductive elimination step with the highest energy while the reductive elimination has the highest energy barrier. By the means of the Activation Strain Model (ASM) of chemical reactivity, it is found that the ketone strain energy released on the oxidative addition does not control the relativity of the OA reactivity, but indeed is the interaction energy between Rh(I) and C-C bond the ruling effect. The effect of the beta-substituents on regioselectivity has been additionally studied.


RSC Advances ◽  
2016 ◽  
Vol 6 (20) ◽  
pp. 16115-16121 ◽  
Author(s):  
Jason E. Camp ◽  
Jay J. Dunsford ◽  
Oliver S. G. Dacosta ◽  
Rebecca K. Blundell ◽  
James Adams ◽  
...  

Renewable sugar-derived palladium(0) nanoparticles (PdNPs) are effective as in situ formed catalysts for cross-coupling reactions in aqueous solutions.


2014 ◽  
Vol 25 (1) ◽  
pp. 166-168 ◽  
Author(s):  
Mojtaba Amini ◽  
Abbas Tarassoli ◽  
Saeed Yousefi ◽  
Sepideh Delsouz-Hafshejani ◽  
Mina Bigdeli ◽  
...  

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