Search results for "ALK"
showing 10 items of 4314 documents
Understanding the mechanism and regioselectivity of the copper(i) catalyzed [3 + 2] cycloaddition reaction between azide and alkyne: a systematic DFT…
2017
The copper(I) catalyzed azide–alkyne [3 + 2] cycloaddition (32CA) reaction and its uncatalyzed version have been studied for systematic understanding of this relevant organic transformation, using DFT calculations at the B3LYP/6-31G(d) (LANL2DZ for Cu) computational levels. In the absence of a copper(I) catalyst, two regioisomeric reaction paths were studied, indicating that the 32CA reaction takes place through an asynchronous one-step mechanism with a very low polar character. The two reactive channels leading to 1,4- and 1,5-regisomer present similar high activation energies of 18.84 and 18.51 kcal mol−1, respectively. The coordination of copper(I) to alkyne produces relevant changes in …
Host–Guest Interactions of Sodiumsulfonatomethyleneresorcinarene and Quaternary Ammonium Halides: An Experimental–Computational Analysis of the Guest…
2020
The molecular recognition of nine quaternary alkyl- and aryl-ammonium halides (Bn) by two different receptors, Calkyl-tetrasodiumsulfonatomethyleneresorcinarene (An), were studied in solution using...
Ion pair complexes and anion binding in the solution of a ditopic receptor.
2016
The synthesis and crystal structures with alkali halides of a ditopic benzo-15-crown-5 bis-urea receptor have been presented. In addition, the anion binding properties of and its alkali metal complexes in solution are presented. A comprehensive single-crystal X-ray crystallographic study of , all together 13 crystal structures, including the ion pair complexes with NaCl, NaBr, NaI, KF, KCl, KBr, KI, RbF, RbCl, and RbI, give a detailed view of how behaves in the solid-state with different alkali halides depending on the size of the cation and anion. In the solid-state forms a 1 : 1 complex with a sodium cation and the anion is complexed as a contact (NaCl) or a separate ion pair (NaBr, NaI).…
Iron-Catalyzed C(sp2)–C(sp3) Cross-Coupling of Chlorobenzenesulfonamides with Alkyl Grignard Reagents: Entry to Alkylated Aromatics
2018
Alkylated benzosulfonamides are compounds of high importance in organic synthesis, including the production of pharmaceuticals, agrochemicals, and plasticizers. We report the iron-catalyzed C(sp2)–C(sp3) cross-coupling of chlorobenzosulfonamides with alkyl Grignard reagents under mild and sustainable conditions. Electronically and sterically varied benzosulfonamides as well as challenging alkyl organometallics containing β-hydrogen afford alkylated benzosulfonamides in high to excellent yields. Sulfonamide represents the most reactive activating group for iron-catalyzed cross-coupling. The process affords alkylated benzenesulfonamides poised for medicinal chemistry applications and traceles…
Coordination Chemistry of Cu2+ Complexes of Small N-Alkylated Tetra-azacyclophanes with SOD Activity
2018
A new tetraaza-pyridinophane macrocycle (L1) N-alkylated with two isopropyl and one methyl groups symmetrically disposed has been prepared and its behavior compared with those of the unsubstituted pyridinophane (L3) and the related compound with three methyl groups (L2). The protonation studies show that, first, a proton binds to the central methylated amine group of L1, while, second protonation leads to a reorganization of the protons that are at this stage attached to the lateral isopropylated amines. The X-ray structure of [HL1]+ agrees with the UV–vis and NMR studies as well as with the results of DFT calculations. The stability of the Cu2+ complexes decreases on increasing the bulkine…
Synthesis, characterisation, and molecular and electronic structure of CpMoCl2(R1C≡CR2) (R1, R2 = Ph, Et, Me): a new class of half-sandwich 17-electr…
2000
International audience; Addition of alkyne to [CpMoCl2]2 affords compounds CpMoCl2(η2-alkyne) (alkyne = EtC[triple bond, length as m-dash]CMe, 1; EtC[triple bond, length as m-dash]CEt, 2; PhC[triple bond, length as m-dash]CMe, 3; PhC[triple bond, length as m-dash]CPh, 4) in good yields. The compounds have been characterised by C,H analyses, IR, EPR and mass spectroscopies, magnetic susceptibility, and cyclic voltammetry. In addition, a single crystal X-ray diffraction analysis has been carried out for compound 4. The alkyne ligand adopts an almost parallel conformation relative to the Cp ring, essentially identical with that of previously reported Nb, Ta, and W analogues. Geometry optimisat…
Combining Neopentyllithium with Potassium tert-Butoxide: Formation of an Alkane-Soluble Lochmann-Schlosser Superbase.
2016
Mixtures of alkyllithium and heavier alkali-metal alkoxides are often used to form alkyl compounds of heavier alkali metals, but these mixtures are also known for their high reactivity in deprotonative metalation reactions. These organometallic mixtures are often called LiC-KOR superbases, but despite many efforts their constitution remains unknown. Herein we present mixed alkali-metal alkyl/alkoxy compounds produced by reaction of neopentyllithium with potassium tert-butoxide. The key to success was the good solubility and temperature-stability of neopentyl alkali-metal compounds, leading to hexane-soluble mixtures, which allowed handling at ambient temperatures and isolation by crystalliz…
Functionalized Dialdehydes as Promising Scaffolds for Access to Heterocycles and β-Amino Acids: Synthesis of Fluorinated Piperidine and Azepane Deriv…
2017
Functionalized dialdehydes are considered important substrates that can be transformed into various substituted heterocyclic, alicyclic, and polysubstituted compounds. Here, we report a robust stereocontrolled procedure for the synthesis of novel functionalized trifluoromethyl-containing piperidine and azepane derivatives, based on oxidative ring cleavage of the C=C bond of diversely substituted cycloalkenes, followed by reductive ring closure of the diformyl intermediates in the presence of fluorine-containing amines.
Selective precipitation of alkyl dihalides using a newly synthesized water-soluble bisphosphorylpillar[5]arene
2016
Bisphosphorylpillar[5]arenes ( and ) were synthesized and used to study the host-guest complexation in organic solvents and water. The interactions between the guests and the phosphate of the hosts lead to strong binding towards alkyl dihalides and alkyldiammonium ions. may be used to detect or separate alkyl dihalides in water due to the rapid precipitation of the complex.
Facile immobilization of copper(I) acetate on silica: A recyclable and reusable heterogeneous catalyst for azide–alkyne clickable cycloaddition react…
2019
Abstract The structurally well-defined copper(I) acetate was immobilized on silica gel via electrostatic interactions. The catalytic activity of the immobilized catalyst Cu(I)–SiO2 was examined in the click synthesis of 1,2,3-triazoles in water/ethanol at room temperature. The catalyst showed high catalytic activity and regioselectivity for the Huisgen [3+2] cycloaddition reaction between terminal alkynes and azides. The catalyst was recovered by simple filtration and reused for up to five times. The analysis of the local electrophilicity/nucleophilicity has been performed on the dinuclear copper–acetylide complex intermediate. Conceptual DFT (CDFT) analysis enabled the explanation of the f…