Modification of multiwalled carbon nanotubes by carboxy groups and determination of the degree of functionalization

Multiwalled carbon nanotubes were modified by carboxy groups. Four independent methods for the determination of the degree of functionalization of the surface were proposed: ¹³C NMR spectroscopy, thermogravimetry, titrimetry, and fluorimetry. The first two methods show the total content of carboxy groups in the sample, and the latter two methods give information about the content of the surface groups only. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 291–295, February, 2008.     

Carboxylation of styrene in the N(C4H9)4Br—heptane system

The carboxylation of styrene into carboxylic acids in the N(C₄H₉)₄Br—heptane system in the presence of phosphine complexes and palladium acetate was studied. In the absence of phosphine, the Pd catalyst seems to be stabilized in solution by forming anionic complexes with NBu₄Br; the stabilization depends on the acidity of the reaction medium. The catalytic system can be used repeatedly, its activity being reduced only slightly.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2458–2461, November, 2004.     

STRUCTURE CHARACTERIZATION AND CATALYTICACTIVITY TEST OF Ni(II) COMPLEXES CONTAINING2-(DIPHENYLPHOSPHINOAMINO) PYRIDINE(PAP)

IntroductionIn1962,N.V.Kutepow'SgroupfirstusedcomplexesofFe,CoandNiascatalyststocatalyzecarboXylationofethanoltopreparepropanoicacidanditsderivants.Thereactionpressurewashighandtheyieldwaslow.LateronPaulalsandhiscolleagueusedabC13andiodineascatalyst,which…     

The First Catalytic Synthesis of an Acrylate from CO2 and an Alkene—A Rational Approach

For more than three decades the catalytic synthesis of acrylates from the cheap and abundantly available C₁ building block carbon dioxide and alkenes has been an unsolved problem in catalysis research, both in academia and industry. Herein, we describe a homogeneous catalyst based on nickel that permits the catalytic synthesis of the industrially highly relevant acrylate sodium acrylate from CO₂, ethylene, and a base, as demonstrated, at this stage, by a turnover number of greater than 10 with respect to the metal.     

Non‐natural Cofactor and Formate‐Driven Reductive Carboxylation of Pyruvate

A non‐natural cofactor and formate driven system for reductive carboxylation of pyruvate is presented. A formate dehydrogenase (FDH) mutant, FDH*, that favors a non‐natural redox cofactor, nicotinamide cytosine dinucleotide (NCD), for generation of a dedicated reducing equivalent at the expense of formate were acquired. By coupling FDH* and NCD‐dependent malic enzyme (ME*), the successful utilization of formate is demonstrated as both CO₂ source and electron donor for reductive carboxylation of pyruvate with a perfect stoichiometry between formate and malate. When ¹³C‐isotope‐labeled formate was used in in vitro trials, up to 53 % of malate had labeled carbon atom. Upon expression of FDH* and ME* in the model host E. coli, the engineered strain produced more malate in the presence of formate and NCD. This work provides an alternative and atom‐economic strategy for CO₂ fixation where formate is used in lieu of CO₂ and offers dedicated reducing power.     

Electroreductive Cobalt‐Catalyzed Carboxylation: Cross‐Electrophile Electrocoupling with Atmospheric CO2

The chemical use of CO₂ as an inexpensive, nontoxic C1 synthon is of utmost topical interest in the context of carbon capture and utilization (CCU). We present the merger of cobalt catalysis and electrochemical synthesis for mild catalytic carboxylations of allylic chlorides with CO₂. Styrylacetic acid derivatives were obtained with moderate to good yields and good functional group tolerance. The thus‐obtained products are useful as versatile synthons of γ‐arylbutyrolactones. Cyclic voltammetry and in operando kinetic analysis were performed to provide mechanistic insights into the electrocatalytic carboxylation with CO₂.     

Advances in Palladium-Catalyzed Carboxylation Reactions

In this short review, we highlight the advancements in the field of palladium-catalyzed carbon dioxide utilization for the synthesis of high value added organic molecules. The review is structured on the basis of the kind of substrate undergoing the Pd-catalyzed carboxylation process. Accordingly, after the introductory section, the main sections of the review will illustrate Pd-catalyzed carboxylation of olefinic substrates, acetylenic substrates, and other substrates (aryl halides and triflates).     

温和条件下金属双氮杂环卡宾配合物催化CO2直接转化为炔酸的高效均相羧化反应

近年来,催化CO2合成精细化学品的研究备受关注。本研究在温和条件下利用金属双氮杂环卡宾催化剂实现CO2与末端炔烃的直接羧化反应,并提出合理的催化机理。首先,合成制备了铜基、银基两种金属双氮杂环卡宾催化剂,实验证明银双氮杂环卡宾配合物具有较好催化活性。通过改变环境条件和底物种类,对反应条件及催化剂底物适应性进行了探究,利用核磁共振谱仪表征产物分子结构并计算直接羧化反应的催化产率。结果表明,适宜催化条件为:1.2eq Cs2CO3作为添加剂、1大气压、室温、无水溶剂和1(mmol)%催化剂用量。银基金属催化剂活性较铜基催化剂高并具有广泛的底物适应性,对苯乙炔的催化产率高达93%;对乙炔气体同样具有良好的催化活性。此类催化剂具有优良的催化活性,能催化合成丙炔酸等重要医药中间体,在工业应用上具有极大潜力和广阔前景。