Search results for "ADD"
showing 10 items of 3360 documents
Cycloaddition reactions of 2H-1-benzothietes and 1,3,5,7-tetrathio-s-indacene-2,6-dithiones
2016
Abstract 2H-1-benzothiete (1) and 2H,5H-benzo[1,2-b:4,5-b′]bisthiete (3) react in form of their open valence isomers with the trithiocarbonic acid esters 2a–c. The one- or twofold cycloaddition reactions yield 1,3-dithiin rings, in which C-2 is a spiro-C atom, that bears four sulfur groups. The bifunctional reactant 3 gives additionally band-shaped, hardly soluble oligomers.
A Molecular Electron Density Theory Study of the Role of the Copper Metalation of Azomethine Ylides in [3 + 2] Cycloaddition Reactions.
2018
The copper metalation of azomethine ylides (AYs) in [3 + 2] cycloaddition (32CA) reactions with electron-deficient ethylenes has been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G(d,p) level, in order to shed light on the electronic effect of the metalation in the course of the reaction. Analysis of the Conceptual Density Functional Theory reactivity indices indicates that the metalation of AYs markedly enhances the nucleophilicity of these species given the anionic character of the AY framework. These 32CA reactions take place through stepwise mechanisms characterized by the formation of a molecular complex. Both nonmetalated and metalated 32CA reactions …
Understanding the Participation of Fluorinated Azomethine Ylides in Carbenoid-Type [3 + 2] Cycloaddition Reactions with Ynal Systems: A Molecular Ele…
2021
The carbenoid-type (cb-type) 32CA reaction of 1,1-difluoroated azomethine ylide (DFAY) with phenylpropynal has been studied using the molecular electron density theory (MEDT). Electron localization function (ELF) characterizes DFAY as a carbenoid species participating in cb-type 32CA reactions. The supernucleophilic character of DFAY and the strong electrophilic character of the ynal cause this polar 32CA reaction to have an unappreciable barrier; the reaction, which is highly exothermic, presents total chemo- and regioselectivity. ELF topological analysis of the bonding changes along the reaction establishes its non-concerted two-stage one-step mechanism, in which the nucleophilic attack o…
Regioselective Synthesis of Mono- and Dispiropyrazoline Derivatives via 1,3-dipolar Cycloaddition with Nitrilimines
2016
The 1,3-dipolar cycloaddition reaction of (E,E)-1,3-bis(arylidene)indan-2-one with diarylnitrilimines, generated in situ via dehydrohalogenation of the corresponding hydrazonoyl chlorides , affords predominantly monospiropyrazolines and as a mixture of diastereoisomers. Also dispiropyrazolines are formed in moderate yields. The structure and stereochemistry of cycloadducts were confirmed by 1H and 13C-NMR spectroscopy, elemental analyses data, and single-crystal X-ray diffraction studies of and .
Cycloaddition of Strained Cyclic Alkenes and Ortho-Quinones : A Distortion/Interaction Analysis
2020
The chemistry of strained unsaturated cyclic compounds has experienced remarkable growth in recent years via the development of metal–free click reactions. Among these reactions, the cycloaddition of cyclopropenes and their analogues to ortho-quinones has been established as a highly promising click reaction. The present work investigates the mechanism involved in the cycloaddition of strained dienes to ortho-quinones and structural factors that would influence this reaction. For this purpose, we use B97D density functional theory calculations throughout, and for relevant cases, we use spin component–scaled MP2 calculations and single–point domain-based local pair natural orbital coupled cl…
Formation of dibutyl carbonate and butylcarbamate via CO2 insertion in titanium(IV) butoxide and reaction with n-butylamine
2016
Abstract The species resulting from insertion of 12CO2 and 13CO2 into titanium(IV) butoxide is for the first time fully characterized by means of infrared and nuclear magnetic resonance spectroscopy. Results show formation of Ti-monobutylcarbonate, that easily undergoes nucleophilic attack by an aliphatic amine. The hydrolysis of the resulting species produces butylcarbamate and dibutylcarbonate as the only main products. Characterization results of the carbonate-like adduct, along with its reactivity with amine molecules open the route to new ways of CO2 utilization as building block for valuable organic compounds.
Theoretical Investigation of the Low-Energy States of CpMoCl(PMe 3 ) 2 and Their Role in the Spin-Forbidden Addition of N 2 and CO
2003
International audience; A recent computational investigation of Jahn−Teller effects in unsaturated 16-electron d4d6 [CpMLn] complexes (Abu-Hasanayn, F.; Cheong, P.; Oliff, M. Angew. Chem.2002, 41, 2120) highlighted the typical presence of two spin-triplet and two singlet states of competing stability in these complexes and pointed out the necessity to account for more than one electronic state in studies thereof. Consequently, we have reinvestigated the addition of N2 to all the four low-energy states of CpMoCl(PH3)2, a reaction for which previously only one singlet and one triplet state have been considered (Keogh, D. W.; Poli, R. J. Am. Chem. Soc.1997, 119, 2516). The present study was pe…
Copper(I)-catalysed regioselective synthesis of pyrazolo[5,1-c]-1,2,4-triazoles: A DFT mechanistic study
2017
Abstract Formation of pyrazolo[5,1-c]-1,2,4-triazoles by means of Cu(I)-catalysed [3+2] cycloaddition (32CA) reactions of C,N-cyclic azomethine imines with phenylacetylene, experimentally reported by Katritzky et al. (JOC 2012, 77, 5813), was studied using the density functional theory (DFT) method. Comparison with the uncatalysed 32CA reaction indicates that the Cu(I) catalyst provides new reaction pathways with lower electronic energy barriers in dichloromethane as solvent. The mechanism proposed by Katritzky for the Cu(I) catalysed reaction is compared with that proposed by Sharpless et al. (JACS 127, 2005, 210). The major difference between these two mechanisms lies in the coordination …
Half-sandwich complexes of molybdenum-(III), -(IV) and -(V) with P–O and P–N bifunctional ligands Ph2PCH2X (X = 2-oxazolinyl, or C(O)NPh2)
2000
International audience; The reaction of the ligands Ph2PCH2X (X = 2-oxazolinyl, I; or C(O)NPh2, II) with the half-sandwich molybdenum(III) precursors [Mo(η-C5R5)(μ-Cl)2]2 (R = H or Me) has been investigated. Ligand I reacts with both complexes to form the corresponding adducts [Mo(η-C5R5)Cl2(Ph2PCH2C3H4NO)] (R = H, 1; or Me, 2). The reaction between I and [MoCp*Cl4] (Cp* = η-C5Me5) affords [MoCp*Cl4(Ph2PCH2C3H4NO-κ1P)] as a kinetic isomer, which then transforms quantitatively to [MoCp*Cl3(Ph2PCH2C3H4NO-κ2P,N)]+Cl−, 3. Ligand II reacts with [MoCp(μ-Cl)2]2 (Cp = η-C5H5) to afford the adduct [CpMoCl2{Ph2PCH2C(O)NPh2-κ2P,O}], 4, as an equilibrium mixture of two isomers. Longer reaction times in…
Total Synthesis of (±)-Scopolamine: Challenges of the Tropane Ring
2016
Scopolamine was synthesized using 6,7-dehydrotropine as a key intermediate. Rhodium-catalyzed [4 + 3] cycloaddition chemistry and a modified Robinson–Schopf reaction were each independently evaluated for their utility in constructing the tropane core. Both synthetic approaches gave comparable overall yields.