What Makes for a Good Catalytic Cycle? A Theoretical Study of the Role of an Anionic Palladium(0) Complex in the Cross-Coupling of an Aryl Halide with an Anionic Nucleophile†

2005 ◽  
Vol 24 (10) ◽  
pp. 2319-2330 ◽  
Author(s):  
Sebastian Kozuch ◽  
Christian Amatore ◽  
Anny Jutand ◽  
Sason Shaik
Keyword(s):  
Theoretical Study ◽  
Aryl Halide ◽  
Cross Coupling ◽  
Catalytic Cycle ◽  
The Cross

The role of H2O in the electron transfer-activation of substrates using SmI2: insights from DFT

2016 ◽  
Vol 45 (9) ◽  
pp. 3706-3710 ◽  
Author(s):  
Xuefei Zhao ◽  
Lionel Perrin ◽  
David J. Procter ◽  
Laurent Maron
Keyword(s):  
Electron Transfer ◽  
Theoretical Study ◽  
Cross Coupling

The first detailed theoretical study on the synthetically important electron transfer reductant SmI2–H2O has been conducted in the context of the activation of important alkyliodide, ketone, lactone and ester substrates, processes of importance in cross-coupling.

The role of magnetic nanoparticles (MNP) as reducing agents in an MNP-supported Pd–catalyst for the reductive homocoupling of aryl halides

2012 ◽  
Vol 90 (1) ◽  
pp. 138-144 ◽  
Author(s):  
Jie Zheng ◽  
Shengyue Lin ◽  
Bi-Wang Jiang ◽  
Todd B. Marder ◽  
Zhen Yang
Keyword(s):  
Magnetic Nanoparticles ◽  
Aryl Halide ◽  
Reducing Power ◽  
Cross Coupling ◽  
Reducing Agent ◽  
Aryl Halides ◽  
Pd Catalyst ◽  
Reductive Homocoupling ◽  
Supported Pd

A palladium pincer catalyst grafted onto the surface of magnetic nanoparticles (MNPs) has been developed. This material effectively catalyzes the reductive homocoupling of various aryl halide substrates, with the MNP support acting as the reducing agent. The catalyst can be recycled up to five times in the absence of additional reducing agent to give almost quantitative yields of biaryl homocoupling products. After the reducing power of the MNP has been depleted, the supported Pd complex remains an effective catalyst for Suzuki–Miyaura cross-coupling.

scholarly journals S13.16 The role of the cross-linked Tyr in the catalytic cycle of cytochrome c oxidase

2008 ◽  
Vol 1777 ◽  
pp. S92
Author(s):  
Elena A. Gorbikova ◽  
Ilya Belevich ◽  
Mårten Wikström ◽  
Michael I. Verkhovsky
Keyword(s):  
Cytochrome C ◽  
Cytochrome C Oxidase ◽  
Catalytic Cycle ◽  
The Cross

On The Remarkably Different Role of Salt in the Cross-Coupling of Arylzincs From That Seen With Alkylzincs

2014 ◽  
Vol 126 (17) ◽  
pp. 4475-4478 ◽  
Author(s):  
Lucas C. McCann ◽  
Michael G. Organ
Keyword(s):  
Cross Coupling ◽  
The Cross

Dual role of nucleophiles in palladium-catalyzed Heck, Stille, and Sonogashira reactions

2004 ◽  
Vol 76 (3) ◽  
pp. 565-576 ◽  
Author(s):  
Anny Jutand
Keyword(s):  
Triple Bond ◽  
Aryl Halide ◽  
Oxidative Addition ◽  
Dual Role ◽  
Catalytic Cycle ◽  
Palladium Catalyzed ◽  
Sonogashira Reactions

In palladium-catalyzed Heck, Stille, or Sonogashira reactions, the nucleophiles-respectively, alkenes, vinylstannanes, or alkynes-are involved in carbopalladation or transmetallation steps that follow the oxidative addition of an aryl halide or triflate to a Pd0 complex. As soon as the nucleophiles possess a C=C or a C 'triple-bond' C bond capable of coordinating the Pd0 complex active in the oxidative addition, they play a dual role since they interfere in the oxidative addition by a decelerating effect due to a partial coordination of the active Pd0 complex. Indeed, its concentration decreases due to the formation of either unreactive complexes (η2-RCH=CH2)Pd0L2 (R = Ph, CO2Et, L = PPh3 ; R = Bu3Sn, L = AsPh3), (η2-RCH=CH2)Pd0L2(OAc)- (R = Ph, L = PPh3), (η2-R-C 'triple-bond' CH)Pd0L2 (R = Ph, L = PPh3) or more slowly reactive complexes (η2-R-C 'triple-bond' CH)Pd0L2 (R = CO2Et, L = PPh3), (η2-RCH=CH2)Pd0L2 (R= CO2Me, L2 = dppf). Whenever the oxidative addition is faster than the ensuing carbopalladation or transmetallation, the decelerating effect of the nucleophiles in the oxidative addition is in favor of a better efficiency for the catalytic cycle by bringing the rate of the fast oxidative addition closer to that of the slow carbopalladation or transmetallation steps.

scholarly journals Nickel versus Palladium in Cross-Coupling Catalysis: On the Role of Substrate Coordination to Zerovalent Metal Complexes

Synthesis ◽  
2019 ◽  
Vol 52 (04) ◽  
pp. 565-573 ◽  
Author(s):  
Alasdair K. Cooper ◽  
Paul M. Burton ◽  
David J. Nelson
Keyword(s):  
Functional Groups ◽  
Density Functional ◽  
Aryl Halide ◽  
Cross Coupling ◽  
Density Functional Theory Calculations ◽  
Detailed Comparison ◽  
Coupling Reactions ◽  
Functional Theory ◽  
Cross Coupling Reactions

A detailed comparison of the effect of coordinating functional groups on the performance of Suzuki–Miyaura reactions catalysed by nickel and palladium is reported, using competition experiments, robustness screening, and density functional theory calculations. Nickel can interact with a variety of functional groups, which manifests as selectivity in competitive cross-coupling reactions. The presence of these functional groups on exogenous additives has effects on cross-coupling reactions that range from a slight improvement in yield to the complete cessation of the reaction. In contrast, palladium does not interact sufficiently strongly with these functional groups to induce selectivity in cross-coupling reactions; the selectivity of palladium-catalysed cross-coupling reactions is predominantly governed by aryl halide electronic properties.

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