铜催化的乙酰苯胺间位碳氢芳基化反应机理的理论研究

通过系统的理论计算研究了Gaunt报道的一个新颖的间位选择性C-H键芳基化反应的机理. Oxycupration机理含有一个关键的Cu(III)基团和酰胺氧原子对苯环C2=C3键的反式加成步. 但是计算结果表明这个反应路径的活化能太高(>175.56 kJ/mol),所以是动力学禁阻的. 提出了一个含有关键的酰胺导向的Cu(III)-Aryl对底物C2=C3键的顺式加成步的机理,这一步是反应的决速步,也是决定产物区域选择性的一步. 这个机理的活化能与实验条件是符合的,而且这个机理预测的产物区域选择性与实验     

XANES/EPR Evidence of the Oxidation of Nickel(II) Quinolinylpropioamide and Its Application in Csp3−H Functionalization

An in situ generated oxidation species of nickel quinolinylpropioamide intermediate was produced. Characterization by X-ray absorption near edge structure (XANES) and EPR provides complementary insights into this oxidized nickel species. With aliphatic amides and isocyanides as substrates, a nickel-catalyzed facile synthesis of structurally diverse five-membered lactams could be achieved.     

Direct C−H Carbamoylation of Nitrogen-Containing Heterocycles

Nucleophilic radical additions at innately electrophilic C(sp²) centers are perfectly suited for the direct functionalization of heterocycles. Using bench stable and commercially available alkyl oxamate and oxamic acid derivatives in combination with photoredox catalysis, a direct carbamoylation of heterocycles yielding amide functionalized pharmacophores in a single step is reported. The reaction conditions reported are compatible with structurally complex heterocyclic substrates of pharmaceutical interest. Notably, derivatives containing functional groups incompatible with standard amidation reactions, such as carboxylic acids and unprotected amines, were found to be amenable to this reaction paradigm.     

Chemical modification of poly(lactic acid) induced by thermal decomposition of N‐acetoxy‐phthalimide during extrusion

Chemical modification of poly(lactic acid) (PLA) with N‐acetoxy‐phthalimide (NAPI) was performed in the melt by reactive extrusion, without using any peroxide initiator. The aminyl and nitroxide radicals produced from the NAPI thermal degradation, were, respectively, used (a) to create PLA macroradicals, and (b) to functionalize the PLA samples through nitroxide radical coupling. Depending on the extrusion temperature and the initial NAPI concentration, grafting rates up to 0.24 mol % were measured, modifying the PLA optical properties. This study represents an original new way of modification of PLA without the use of conventional peroxide initiators. Indeed, the undesirable side reactions (PLA branching or crosslinking) usually observed when using peroxides to initiate the radical grafting of PLA were avoided when using NAPI. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 120–129     

Iodine-Promoted Domino Oxidative Cyclization for the One-Pot Synthesis of Novel Fused Four-Ring Quinoxaline Fluorophores by sp3 C−H Functionalization

A method for the synthesis of novel fused four-ring quinoxaline skeleton has been described by an I₂ promoted sp³ C−H functionalization between 1,2,3,3-tetramethyl-3H-indolium iodides and 1,2-diamines. This transformation proceeds smoothly under metal- and peroxide-free conditions through a sequential iodination, oxidation, annulation and rearrangement. Moreover, 8,9-dichloro-5,12,12-trimethyl-2-(trifluoromethyl)-5,12-dihydroquinolino[2,3-b]quinoxaline showed good photophysical properties and was used in live cell imaging, indicating the potential value of this skeleton as a fluorophore in probes.     

Remote Fluorination and Fluoroalkyl(thiol)ation Reactions

Remote functionalization reactions have the power to transform a C−H (or C−C) bond at a distant position from a functional group. This Review summarizes recent advances and key breakthroughs in remote fluorination, trifluoromethylation, difluoromethylation, trifluoromethylthiolation, and fluoroalkenylation reactions. Several powerful strategies have emerged to control the reactivity and distal selectivity such as the undirected radical approach, the 1,5-hydrogen atom transfer, the metal migration, the use of distant directing groups, and the ring-opening reactions. These unconventional and predictable C−H (and C−C) functionalization transformations should allow for the preparation of a wide range of otherwise-difficult-to-access alkyl, aromatic, heteroaromatic, and structurally complex fluorides.     

Palladium-catalyzed direct allylation of fluorinated benzothiadiazoles with allyl chlorides

A palladium catalyzed cross-coupling of fluorinated benzothiadiazoles (FBTs) with allyl chlorides is reported. The significant feature of this method is synthetic simplicity, providing a straightforward access to unsymmetrical and symmetrical alkylated FBT derivatives that are of interest in organic electronic and optoelectronic materials.     

Ultrasonic assisted functionalization of MWCNT and synergistic electrocatalytic effect of nano-hydroxyapatite incorporated MWCNT-chitosan scaffolds for sensing of nitrofurantoin

In the present work, we report the fabrication of stable composite of chitosan hydrogels (CHI) on multiwalled carbon nanotubes (MWCNT) using a simple ultrasonic-assisted method. Also, rod-like hydroxyapatite nanoparticles (HA NPs) were synthesised using a hydrothermal route and were incorporated into the highly conductive MWCNT-CHI scaffolds using an ultrasonication method. The functionalization of MWCNT and preparation of HA NPs on MWCNT-CHI nanocomposite were done using the sonication over the frequency of 37 kHz with the ultrasonic power capable of 150 W (Elmasonic Easy 60H bath sonicator). The resulting hybrid HA NPs/MWCNT-CHI nanocomposites have an excellent surface area and high surface to volume ratio, which leads to the sensitive detection of nitrofurantoin than pristine MWCNT and HA NPs. The complete elemental and morphological analyses of the HA NPs/MWCNT-CHI nanocomposites were characterised by XRD, FTIR, RAMAN, FESEM, TEM, EDX, and elemental mapping techniques. Electrochemical analysis of the HA NPs/MWCNT-CHI nanocomposites was carried out by cyclic voltammetry, electrochemical impedance spectroscopy and amperometry methods. The modified glassy carbon electrode (GCE) of HA NPs/MWCNT-CHI nanocomposites exhibit the nitrofurantoin detection activity at the linear range of 0.005–982.1 µM with the detection limit of 1.3 nM. The synergistic electrocatalytic activity of HA NPs/MWCNT-CHI nanocomposites modified GCE is correlated to the sensitivity of 0.16 µAµM⁻¹ cm⁻² with excellent precision and accuracy towards the sensing of nitrofurantoin.     

Synthesis and characterization of water-soluble carbon nanotubes from mustard soot

Carbon nanotubes (CNT) has been synthesized by pyrolysing mustard oil using an oil lamp. It was made water-soluble (wsCNT) through oxidative treatment by dilute nitric acid and was characterized by SEM, AFM, XRD, Raman and FTIR spectroscopy. The synthesized wsCNT showed the presence of several junctions and defects in it. The presence of curved graphene structure (sp²) with frequent sp³ hybridized carbon is found to be responsible for the observed defects. These defects along with the presence of di- and tri-podal junctions showed interesting magnetic properties of carbon radicals formed by spin frustration. This trapped carbon radical showed ESR signal in aqueous solution and was very stable even under drastic treatment by strong oxidizing or reducing agents. Oxidative acid treatment of CNT introduced several carboxylic acid group functionalities in wsCNT along with the nicking of the CNT at different lengths with varied molecular weight. To evaluate molecular weights of these wsCNTs, an innovative method like gel electrophoresis using high molecular weight DNA as marker was introduced.