- Visible-light photoredox-catalyzed selective carboxylation of C(sp3)?F bonds with CO2
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It is highly attractive and challenging to utilize carbon dioxide (CO2), because of its inertness, as a nontoxic and sustainable C1 source in the synthesis of valuable compounds. Here, we report a novel selective carboxylation of C(sp3)?F bonds with CO2 via visible-light photoredox catalysis. A variety of mono-, di-, and trifluoroalkylarenes as well as α,α-difluorocarboxylic esters and amides undergo such reactions to give important aryl acetic acids and α-fluorocarboxylic acids, including several drugs and analogs, under mild conditions. Notably, mechanistic studies and DFT calculations demonstrate the dual role of CO2 as an electron carrier and electrophile during this transformation. The fluorinated substrates would undergo single-electron reduction by electron-rich CO2 radical anions, which are generated in situ from CO2 via sequential hydride-transfer reduction and hydrogen-atom-transfer processes. We anticipate our finding to be a starting point for more challenging CO2 utilization with inert substrates, including lignin and other biomass.
- Bo, Zhi-Yu,Chen, Lin,Gao, Tian-Yu,Jing, Ke,Lan, Yu,Liu, Shi-Han,Luo, Shu-Ping,Yan, Si-Shun,Yu, Bo,Yu, Da-Gang
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supporting information
p. 3099 - 3113
(2021/11/16)
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- Visible-Light-Driven Reductive Carboarylation of Styrenes with CO2 and Aryl Halides
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The first example of visible-light-driven reductive carboarylation of styrenes with CO2 and aryl halides in a regioselective manner has been achieved. A broad range of aryl iodides and bromides were compatible with this reaction. Moreover, pyridyl halides, alkyl halides, and even aryl chlorides were also viable with this method. These findings may stimulate the exploration of novel visible-light-driven Meerwein arylation-addition reactions with user-friendly aryl halides as the radical sources and the photocatalytic utilization of CO2
- Gao, Yuzhen,Li, Gang,Wang, Hao,Zhou, Chunlin
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supporting information
p. 8122 - 8129
(2020/05/20)
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- Method for synthesizing succinic acid compounds
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The invention provides a method for synthesizing succinic acid compounds. The method specifically comprises the following steps: adding a substrate, a photocatalyst and an alkali into a reaction tube,adding a reducing agent and a solvent under the atmosphere of CO2, conducting reacting under the irradiation of visible light, carrying out quenching treatment after the raw materials react completely, and then conducting separating and purifying to obtain a dicarboxylated product of olefin, namely a succinic acid compound. The photocatalyst is 4CzIPN or Ir[(ppy)2(dtbppy)]PF6 and the like, and the reaction substrate comprises 1,1-diaryl ethylene, a monoaryl substituted olefin compound, an acrylate compound and allene. According to the scheme provided by the invention, the reaction conditionsare mild, the applicability of the reaction substrate is wide, and the yield is basically not influenced under the condition that the reaction substrate is amplified to the gram scale; and meanwhile,the invention overcomes the defects of high toxicity of reagents and harsh reaction conditions in the prior art, and has a good industrial application prospect.
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Paragraph 0028-0036; 0038; 0045-0047; 0049
(2019/08/01)
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- Solvatochromic and quantum chemical investigations of newly synthesized succinimides: Substituent effect on intramolecular charge transfer
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Two series of 1-aryl-3-phenyl- and 1-aryl-3,3-diphenylpyrrolidine-2,5- diones were synthesized and their solvatochromic properties were studied in a set of 15 solvents of different polarity. The effect of specific and non-specific solvent-solute interacti
- Banjac, Neboj?a,Tri?ovi?, Nemanja,Vitnik, ?eljko,Vitnik, Vesna,Valenti?, Nata?a,U??umli?, Gordana,Jurani?, Ivan
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p. 1525 - 1535
(2013/10/22)
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- Efficient electrochemical dicarboxylation of phenyl-substituted alkenes: Synthesis of 1-phenylalkane-1,2-dicarboxylic acids
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Electrochemical dicarboxylation of phenyl-substituted alkenes in the presence of atmospheric pressure of carbon dioxide with a platinum plate cathode and a magnesium rod anode readily took place efficiently in a DMF solution containing 0.1 M Et4NClO4 to give the corresponding 1,2-dicarboxylic acids in high yields.
- Senboku,Komatsu,Fujimura,Tokuda
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p. 418 - 420
(2007/10/03)
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- Synthesis of some N-Acyl Derivatives of Optically Active 1,2-Aminoalkanols
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New N-acyl derivatives of (R,S) and (S)-(+)-1-amino-2-propanol as well as (R,S) and (S)-(+)-1-amino-2-butanol 1-8 having potential anticonvulsant activity were obtained by acylation of appropriate 1,2-aminoalkanol with 3,3-diphenyl-2,5-diketopyrrolidine-1
- Gajewczyk, L.,Marona, H.
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p. 876 - 880
(2007/10/02)
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- Reaction of Dilithiated Carboxylic Acids with Iodine: Evidence for the Formation of a Radical Anion Intermediate
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The mechanism for oxidative dimerization of carboxylic acid dianions involves single electron transfer to iodine, producing an organic anion radical.Rearrangement of this species was observed with suitable substrates at a rate competitive with intermolecular reactions.The radical anion can dimerize or react with iodine.The iodide thus generated can be isolated (reaction with excess of iodine) or can participate in a polar SN2-type reaction sequence leading to dimeric products (reaction with 1/2 equiv of iodine).The interference by free amines (liberated during the metalation with lithium amides) is rationalized by the formation of a charge-transfer complex with iodine which decomposes, liberating protons.
- Renaud, Philippe,Fox, Marye Anne
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p. 3745 - 3752
(2007/10/02)
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- α,α-Diphenylsuccinimide: Evaluation of anticonvulsant and hydrophobic properties
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The anticonvulsant potencies (ED50) of α,α-diphenylsuccinimide, phenytoin, and phenobarbital were evaluated in mice by a standard maximal electroshock technique. Potencies were expressed in terms of intraperitoneal dosage and blood and brain co
- Jones,Amato,Jones
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p. 310 - 313
(2007/10/02)
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