Synthesis of Arylated Perylene Bisimides through C−H Bond Cleavage under Ruthenium Catalysis

2009 ◽  
Vol 11 (23) ◽  
pp. 5426-5429 ◽  
Author(s):  
Satomi Nakazono ◽  
Shanmugam Easwaramoorthi ◽  
Dongho Kim ◽  
Hiroshi Shinokubo ◽  
Atsuhiro Osuka
ChemInform ◽  
2013 ◽  
Vol 44 (21) ◽  
pp. no-no
Author(s):  
Yuto Hashimoto ◽  
Koji Hirano ◽  
Tetsuya Satoh ◽  
Fumitoshi Kakiuchi ◽  
Masahiro Miura

2012 ◽  
Vol 78 (2) ◽  
pp. 638-646 ◽  
Author(s):  
Yuto Hashimoto ◽  
Koji Hirano ◽  
Tetsuya Satoh ◽  
Fumitoshi Kakiuchi ◽  
Masahiro Miura

Catalysts ◽  
2019 ◽  
Vol 9 (2) ◽  
pp. 173 ◽  
Author(s):  
Keisham Singh

The past decades have witnessed rapid development in organic synthesis via catalysis, particularly the reactions through C–H bond functionalization. Transition metals such as Pd, Rh and Ru constitute a crucial catalyst in these C–H bond functionalization reactions. This process is highly attractive not only because it saves reaction time and reduces waste,but also, more importantly, it allows the reaction to be performed in a highly region specific manner. Indeed, several organic compounds could be readily accessed via C–H bond functionalization with transition metals. In the recent past, tremendous progress has been made on C–H bond functionalization via ruthenium catalysis, including less expensive but more stable ruthenium(II) catalysts. The ruthenium-catalysed C–H bond functionalization, viz. arylation, alkenylation, annulation, oxygenation, and halogenation involving C–C, C–O, C–N, and C–X bond forming reactions, has been described and presented in numerous reviews. This review discusses the recent development of C–H bond functionalization with various ruthenium-based catalysts. The first section of the review presents arylation reactions covering arylation directed by N–Heteroaryl groups, oxidative arylation, dehydrative arylation and arylation involving decarboxylative and sp3-C–H bond functionalization. Subsequently, the ruthenium-catalysed alkenylation, alkylation, allylation including oxidative alkenylation and meta-selective C–H bond alkylation has been presented. Finally, the oxidative annulation of various arenes with alkynes involving C–H/O–H or C–H/N–H bond cleavage reactions has been discussed.


2020 ◽  
Author(s):  
Shubham Deolka ◽  
Orestes Rivada Wheelaghan ◽  
Sandra Aristizábal ◽  
Robert Fayzullin ◽  
Shrinwantu Pal ◽  
...  

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.


2020 ◽  
Author(s):  
Lucas A. Freeman ◽  
Akachukwu D. Obi ◽  
Haleigh R. Machost ◽  
Andrew Molino ◽  
Asa W. Nichols ◽  
...  

The reduction of the relatively inert carbon–oxygen bonds of CO<sub>2</sub> to access useful CO<sub>2</sub>-derived organic products is one of the most important fundamental challenges in synthetic chemistry. Facilitating this bond-cleavage using earth-abundant, non-toxic main group elements (MGEs) is especially arduous because of the difficulty in achieving strong inner-sphere interactions between CO<sub>2</sub> and the MGE. Herein we report the first successful chemical reduction of CO<sub>2</sub> at room temperature by alkali metals, promoted by a cyclic(alkyl)(amino) carbene (CAAC). One-electron reduction of CAAC-CO<sub>2</sub> adduct (<b>1</b>) with lithium, sodium or potassium metal yields stable monoanionic radicals clusters [M(CAAC–CO<sub>2</sub>)]<sub>n</sub>(M = Li, Na, K, <b> 2</b>-<b>4</b>) and two-electron alkali metal reduction affords open-shell, dianionic clusters of the general formula [M<sub>2</sub>(CAAC–CO<sub>2</sub>)]<sub>n </sub>(<b>5</b>-<b>8</b>). It is notable that these crystalline clusters of reduced CO<sub>2</sub> may also be isolated via the “one-pot” reaction of free CO<sub>2</sub> with free CAAC followed by the addition of alkali metals – a reductive process which does not occur in the absence of carbene. Each of the products <b>2</b>-<b>8</b> were investigated using a combination of experimental and theoretical methods.<br>


2018 ◽  
Author(s):  
Lucie Nurdin ◽  
Denis M. Spasyuk ◽  
Laura Fairburn ◽  
Warren Piers ◽  
Laurent Maron

Diprotonation of a remarkably stable, toluene soluble cobalt peroxo complex supported by a neutral, dianionic pentadentate ligand leads to facile O-O bond cleavage and production of a highly reactive Co(IV) oxyl cation intermediate that dimerizes and releases O<sub>2</sub>. These processes are relevant to both O<sub>2</sub> reduction and O<sub>2</sub> evolution and the mechanism was probed in detail both experimentally and computationally.


2019 ◽  
Author(s):  
Katsutoshi Sato ◽  
Shin-ichiro Miyahara ◽  
Yuta Ogura ◽  
Kotoko Tsujimaru ◽  
Yuichiro Wada ◽  
...  

<p>To mitigate global problems related to energy and global warming, it is helpful to develop an ammonia synthesis process using catalysts that are highly active under mild conditions. Here we show that the ammonia synthesis activity of Ru/Ba/LaCeO<i><sub>x</sub></i> pre-reduced at 700 °C is the highest reported among oxide-supported Ru catalysts. Our results indicate that low crystalline oxygen-deficient composite oxides, which include Ba<sup>2+</sup>, Ce<sup>3+</sup> and La<sup>3+</sup>, with strong electron-donating ability, accumulate on Ru particles and thus promote N≡N bond cleavage, which is the rate determining step for ammonia synthesis.</p>


2019 ◽  
Author(s):  
Katsutoshi Sato ◽  
Shin-ichiro Miyahara ◽  
Yuta Ogura ◽  
Kotoko Tsujimaru ◽  
Yuichiro Wada ◽  
...  

<p>To mitigate global problems related to energy and global warming, it is helpful to develop an ammonia synthesis process using catalysts that are highly active under mild conditions. Here we show that the ammonia synthesis activity of Ru/Ba/LaCeO<i><sub>x</sub></i> pre-reduced at 700 °C is the highest reported among oxide-supported Ru catalysts. Our results indicate that low crystalline oxygen-deficient composite oxides, which include Ba<sup>2+</sup>, Ce<sup>3+</sup> and La<sup>3+</sup>, with strong electron-donating ability, accumulate on Ru particles and thus promote N≡N bond cleavage, which is the rate determining step for ammonia synthesis.</p>


2019 ◽  
Author(s):  
Bella Grigorenko ◽  
Igor Polyakov ◽  
Alexander Nemukhin

<p>We report a mechanism of adenosine triphosphate (ATP) to cyclic adenosine monophosphate (cAMP) conversion by the mammalian type V adenylyl cyclase revealed in molecular dynamics (MD) and quantum mechanics/molecular mechanics (QM/MM) simulations. We characterize a set of computationally derived enzyme-substrate (ES) structures showing an important role of coordination shells of magnesium ions in the solvent accessible active site. Several stable six-fold coordination shells of Mg<sub>A</sub><sup>2+ </sup>are observed in MD simulations of ES complexes. In the lowest energy ES conformation, the coordination shell of Mg<sub>A</sub><sup>2+ </sup>does not include the O<sub>δ1</sub> atom of the conserved Asp440 residue. Starting from this conformation, a one-step reaction mechanism is characterized which includes proton transfer from the ribose O<sup>3'</sup>H<sup>3' </sup>group in ATP to Asp440 via a shuttling water molecule and P<sup>A</sup>-O<sup>3A</sup> bond cleavage and O<sup>3'</sup>-P<sup>A</sup> bond formation. The energy profile of this route is consistent with the observed reaction kinetics. In a higher energy ES conformation, Mg<sub>A</sub><sup>2+</sup> is bound to the O<sub>δ1</sub>(Asp440) atom as suggested in the relevant crystal structure of the protein with a substrate analog. The computed energy profile initiated by this ES is characterized by higher energy expenses to complete the reaction. Consistently with experimental data, we show that the Asp440Ala mutant of the enzyme should exhibit a reduced but retained activity. All considered reaction pathways include proton wires from the O<sup>3'</sup>H<sup>3' </sup>group via shuttling water molecules. </p>


2020 ◽  
Vol 24 (18) ◽  
pp. 2181-2191
Author(s):  
Li Wang ◽  
Ziyi Li ◽  
Jiang Liu ◽  
Jianlin Han ◽  
Hiroki Moriwaki ◽  
...  

The development of an efficient and mild synthetic methodology for the construction of bioactive fluorine-containing molecules represents one of the hot research topics in general synthetic organic chemistry. In this review, some recent progresses achieved in the development of detrifluoroacetylatively generated mono-fluorinated enolates via CC bond cleavage and their asymmetric nucleophilic reactions for assembly of chiral quaternary C-F center containing compounds.


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