Nickel-Catalyzed α-Arylation of Zinc Enolates with Polyfluoroarenes via C–F Bond Activation under Neutral Conditions

2014 ◽  
Vol 16 (21) ◽  
pp. 5544-5547 ◽  
Author(s):  
Daohong Yu ◽  
Chang-Sheng Wang ◽  
Cheng Yao ◽  
Qilong Shen ◽  
Long Lu
Keyword(s):  
Bond Activation ◽  
Zinc Enolates ◽  
Neutral Conditions

ChemInform Abstract: Nickel-Catalyzed α-Arylation of Zinc Enolates with Polyfluoroarenes via C-F Bond Activation under Neutral Conditions.

ChemInform ◽  
2015 ◽  
Vol 46 (17) ◽  
pp. no-no
Author(s):  
Daohong Yu ◽  
Chang-Sheng Wang ◽  
Cheng Yao ◽  
Qilong Shen ◽  
Long Lu
Keyword(s):  
Bond Activation ◽  
Zinc Enolates ◽  
Neutral Conditions

α-Arylation of Zinc Enolates via C–F Bond Activation

Synfacts ◽  
2015 ◽  
Vol 11 (02) ◽  
pp. 0184-0184
Keyword(s):  
Bond Activation ◽  
Zinc Enolates

Regioselective and Room-Temperature Carbon–Carbon Bond Activation of Cyclopropanes by Rhodium(II) Porphyrin

Synlett ◽  
2017 ◽  
Vol 29 (06) ◽  
pp. 759-763 ◽  
Author(s):  
Kin Chan ◽  
Shiyu Feng
Keyword(s):  
Functional Groups ◽  
Room Temperature ◽  
Bond Activation ◽  
Carbon Bond ◽  
Carbon Carbon Bond ◽  
Neutral Conditions

Regioselective carbon–carbon bond activation of cyclopropanes by RhII(tmp) (tmp = 5,10,15,20-tetramesitylporphyrinato dianion) was achieved at room temperature under neutral conditions to yield corresponding rhodium–porphyrin alkyls. This reaction can tolerate water, and functional groups are compatible.

Metal-Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes

2020 ◽  
Author(s):  
Shubham Deolka ◽  
Orestes Rivada Wheelaghan ◽  
Sandra Aristizábal ◽  
Robert Fayzullin ◽  
Shrinwantu Pal ◽  
...  
Keyword(s):  
Alkyl Group ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Terminal Alkyne ◽  
Alkyl Aryl ◽  
Metal Metal ◽  
The Stability ◽  
Selective Formation ◽  
Organoplatinum Compounds

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

Imine as a Linchpin Approach for Distal C(sp2)–H Functionalization

2020 ◽  
Author(s):  
Sukdev Bag ◽  
Sadhan Jana ◽  
Sukumar Pradhan ◽  
Suman Bhowmick ◽  
Nupur Goswami ◽  
...  
Keyword(s):  
Organic Molecules ◽  
Bond Activation ◽  
Bond Formation ◽  
Ancillary Ligand ◽  
Significant Challenge ◽  
Site Selectivity ◽  
Directing Group ◽  
Covalently Linked ◽  
Complex Organic ◽  
Post Functionalization

<p>Despite the widespread applications of C–H functionalization, controlling site selectivity remains a significant challenge. Covalently attached directing group (DG) served as an ancillary ligand to ensure proximal <i>ortho</i>-, distal <i>meta</i>- and <i>para</i>-C-H functionalization over the last two decades. These covalently linked DGs necessitate two extra steps for a single C–H functionalization: introduction of DG prior to C–H activation and removal of DG post-functionalization. We introduce here a transient directing group for distal C(<i>sp<sup>2</sup></i>)-H functionalization <i>via</i> reversible imine formation. By overruling facile proximal C-H bond activation by imine-<i>N</i> atom, a suitably designed pyrimidine-based transient directing group (TDG) successfully delivered selective distal C-C bond formation. Application of this transient directing group strategy for streamlining the synthesis of complex organic molecules without any necessary pre-functionalization at the distal position has been explored.</p>

Pt-Pd Nanoalloy for the Unprecedented Activation of Carbon-Fluorine Bond at Low Temperature

2019 ◽  
Author(s):  
Raghu Nath Dhital ◽  
keigo nomura ◽  
Yoshinori Sato ◽  
Setsiri Haesuwannakij ◽  
Masahiro Ehara ◽  
...  
Keyword(s):  
Activation Energy ◽  
Low Temperature ◽  
Dft Calculations ◽  
Bond Activation ◽  
Mild Conditions ◽  
Selective Transformation ◽  
Rate Determining Step ◽  
Highly Active ◽  
Harsh Conditions ◽  
Reaction Profile

Carbon-Fluorine (C-F) bonds are considered the most inert organic functionality and their selective transformation under mild conditions remains challenging. Herein, we report a highly active Pt-Pd nanoalloy as a robust catalyst for the transformation of C-F bonds into C-H bonds at low temperature, a reaction that often required harsh conditions. The alloying of Pt with Pd is crucial to activate C-F bond. The reaction profile kinetics revealed that the major source of hydrogen in the defluorinated product is the alcoholic proton of 2-propanol, and the rate-determining step is the reduction of the metal upon transfer of the <i>beta</i>-H from 2-propanol. DFT calculations elucidated that the key step is the selective oxidative addition of the O-H bond of 2-propanol to a Pd center prior to C-F bond activation at a Pt site, which crucially reduces the activation energy of the C-F bond. Therefore, both Pt and Pd work independently but synergistically to promote the overall reaction

A Self-Trapping, Bipolar Viologen Bromide Electrolyte for Aqueous Redox Flow Batteries

2020 ◽  
Author(s):  
wenda wu ◽  
Jian Luo ◽  
Fang Wang ◽  
Bing Yuan ◽  
Tianbiao Liu
Keyword(s):  
Redox Flow Battery ◽  
Capacity Retention ◽  
Redox Flow Batteries ◽  
Redox Electrolyte ◽  
Charge Process ◽  
Self Trapping ◽  
Flow Batteries ◽  
Total Capacity ◽  
Neutral Conditions ◽  
Low Solubility

Aqueous organic redox flow batteries (AORFBs) have become increasing attractive for scalable energy storage. However, it remains challenging to develop high voltage, powerful AORFBs because of the lack of catholytes with high redox potential. Herein, we report methyl viologen dibromide (<b>[MV]Br<sub>2</sub></b>) as a facile self-trapping, bipolar redox electrolyte material for pH neutral redox flow battery applications. The formation of the <b>[MV](Br<sub>3</sub>)<sub>2</sub></b> complex was computationally predicted and experimentally confirmed. The low solubility <b>[MV](Br<sub>3</sub>)<sub>2</sub></b> complex in the catholyte during the battery charge process not only mitigates the crossover of charged tribromide species (Br<sub>3</sub><sup>-</sup>) and addresses the toxicity concern of volatile bromine simultaneously. A 1.53 V bipolar MV/Br AORFB delivered outstanding battery performance at pH neutral conditions, specifically, 100% total capacity retention, 133 mW/cm<sup>2</sup> power density, and 60% energy efficiency at 40 mA/cm<sup>2</sup>.

Ni(0)-Catalyzed α-Allylic Alkylation of Regular Ketones with 1,3-Dienes under pH and Redox-neutral Conditions

2019 ◽  
Author(s):  
Tiantian Chen ◽  
Yang Yang ◽  
Liyu Xie ◽  
Haijian Yang ◽  
Guangbin Dong ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Dual Role ◽  
Allylic Alkylation ◽  
Cross Coupling Reaction ◽  
Neutral Conditions

<p>We report a Ni(0)-catalyzed cross coupling reaction between simple ketones and 1,3-dienes. A variety of a-allylic alkylation products were formed in an 1,2-addition manner with excellent regioselectivity. Water was found to significantly accelerate this transformation. A HO-Ni-H species generated from oxidative addition of Ni(0) to H<sub>2</sub>O is proposed to play a “dual role” in activating both the ketone and the diene substrate.</p>

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