Iron-Mediated C-C Bond Formation. Preparation of (Trimethylenemethane)iron Complexes via Reaction of Weak Carbon Nucleophiles with in Situ Generated Cross-Conjugated Pentadienyl Cations. Nucleophilic Attack on (Trimethylenemethane)iron Complexes with Carbanions

1995 ◽  
Vol 60 (6) ◽  
pp. 1611-1618 ◽  
Author(s):  
William A. Donaldson ◽  
M. Azad Hossain ◽  
Charles D. Cushnie
2020 ◽  
Author(s):  
Roman Ezhov ◽  
Alireza Ravari ◽  
Gabriel Bury ◽  
Paul Smith ◽  
Yulia Pushkar

Abstract Development of economically viable artificial photosynthesis requires use of 3d metal-based catalysts. Water oxidation by [Co4O4]n+ cubane mimics water splitting by CaMn4O5 cluster in Nature but the exact mechanism of O-O bond formation is presently unknown. We demonstrate first in situ detection CoIV=O (~ 1.67 Å) moiety formed upon activation of [Co4O4Py4Ac4]0 (Py = pyridine and Ac = CH3COO−) towards O-O bond formation. Combined spectroscopic and DFT analyses show that the intermediate active in O-O bond formation has two CoIV centers and at least one CoIV=O unit of strong radicaloid character that participates in O-O bond formation via water nucleophilic attack. The multimetallic structure of the cubane provides unique stabilization for CoIV=O + H2O = Co-OOH + H+ transition with the carboxyl accepting the proton and the bridging oxygen stabilizing the peroxide via hydrogen bonding. Results are important for development of oxygen evolution catalysts based on Earth-abundant 3d elements.


2019 ◽  
Author(s):  
Leiyang Lv ◽  
Dianhu Zhu ◽  
Zihang Qiu ◽  
Jianbin Li ◽  
Chao-Jun Li

Hydroalkylation of unsaturated hydrocarbons with unstablized carbon nucleophiles is difficult and remains a major challenge. The disclosed examples so far mainly focused on the involvement of heteroatom and/or stabilized carbon nucleophiles as efficient reaction partners. Reported here is an unprecedented regioselective nickel-catalyzed hydroalkylation of 1,3-dienes with hydrazones, generated in situ from abundant aryl aldehydes and ketones and acted as both the sources of unstabilized carbanions and hydride. With this strategy, both terminal and sterically hindered internal dienes are hydroalkylated efficiently in a highly selective manner, thus providing a novel and reliable catalytic method to construct challenging C(sp3)-C(sp3) bonds.


2016 ◽  
Vol 113 (28) ◽  
pp. 7722-7726 ◽  
Author(s):  
Gavin O. Jones ◽  
Alexander Yuen ◽  
Rudy J. Wojtecki ◽  
James L. Hedrick ◽  
Jeannette M. García

It is estimated that ∼2.7 million tons poly(carbonate)s (PCs) are produced annually worldwide. In 2008, retailers pulled products from store shelves after reports of bisphenol A (BPA) leaching from baby bottles, reusable drink bottles, and other retail products. Since PCs are not typically recycled, a need for the repurposing of the PC waste has arisen. We report the one-step synthesis of poly(aryl ether sulfone)s (PSUs) from the depolymerization of PCs and in situ polycondensation with bis(aryl fluorides) in the presence of carbonate salts. PSUs are high-performance engineering thermoplastics that are commonly used for reverse osmosis and water purification membranes, medical equipment, as well as high temperature applications. PSUs generated through this cascade approach were isolated in high purity and yield with the expected thermal properties and represent a procedure for direct conversion of one class of polymer to another in a single step. Computational investigations performed with density functional theory predict that the carbonate salt plays two important catalytic roles in this reaction: it decomposes the PCs by nucleophilic attack, and in the subsequent polyether formation process, it promotes the reaction of phenolate dimers formed in situ with the aryl fluorides present. We envision repurposing poly(BPA carbonate) for the production of value-added polymers.


2006 ◽  
Vol 118 (32) ◽  
pp. 5490-5494 ◽  
Author(s):  
K. C. Nicolaou ◽  
Anthony A. Estrada ◽  
Sang Hyup Lee ◽  
Graeme C. Freestone
Keyword(s):  

ChemInform ◽  
2009 ◽  
Vol 40 (44) ◽  
Author(s):  
Remi Martinez ◽  
Marc-Olivier Simon ◽  
Reynald Chevalier ◽  
Cyrielle Pautigny ◽  
Jean-Pierre Genet ◽  
...  

ChemInform ◽  
2012 ◽  
Vol 43 (24) ◽  
pp. no-no
Author(s):  
Hiromichi Fujioka ◽  
Kenzo Yahata ◽  
Tomohito Hamada ◽  
Ozora Kubo ◽  
Takashi Okitsu ◽  
...  

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