Search results for "cycloaddition"

N-Heterocyclic Carbene Catalyzed [3+2] Cycloaddition of Enals with Masked Cinnamates for the Asymmetric One-Pot Synthesis of Adipic Acid Derivatives.

2017

A novel short entry to 3,4-disubstituted adipic acids has been developed by employing an asymmetric NHC-catalyzed [3+2] cycloaddition of enals with masked cinnammates in moderate to good yields and high stereoselectivities. The synthetic utility of the protocol was demonstrated by the basic conversion of the masked cyclopentanone intermediates to 3S,4S-disubstituted adipic acid precursors of pharmaceutically important gababutins.

Unveiling the Chemo‐ and Regioselectivity of the [3+2] Cycloaddition Reaction between 4‐Chlorobenzonitrile Oxide and β‐Aminocinnamonitrile with a MED…

2021

A bis(triazole)benzamide receptor for the complexation of halide anions and neutral carboxylic acid guests. Guest-controlled topicity and self-assemb…

2012

Bis(triazole)benzamide 1 has been readily synthesized by means of Cu-catalyzed 1,3-dipolar cycloaddition and its ability to bind halide anions and neutral gallic acid derivative 12GA has been theoretically and experimentally investigated. The cavity defined by the N-H amide group and the vicinal aromatic hydrogens is suitable to form H-bonding arrays with halide guests. The stability of complexes 1·Cl- and 1·Br- is very similar, as DFT calculations predict and 1H NMR titration experiments confirm. The zigzag "anti" conformation of the molecule generates two regions with complementary positive and negative potentials that favor the statistical complexation of two molecules of the neutral car…

Synthesis, characterization and X-ray structure of glycosyl-1,2-isoxazoles and glycosyl-1,2-isoxazolines prepared via 1,3-dipolar cycloaddition

2013

Abstract A convenient preparative method of a series of glycosyl-1,2-isoxazoles ( 6–11 ) and glycosyl-1,2-isoxazolines ( 15–20 ) by a simple and efficient 1,3-dipolar cycloaddition of a series of aryl nitrile oxide, generated in situ from aryl oximes ( 4–5 ), with a variety of O -propargyl glycosyles ( 1 – 3 ) or O -allyl glycosyles ( 12–14 ) respectively, is reported. The carbohydrate-containing 1,2-isoxazoles and 1,2-isoxazolines compounds were isolated in excellent yields (81–91%) and they were fully characterized by 1 H, 13 C NMR and mass spectrometry. The relative stereochemistry of the glycosyl-1,2-isoxazole 10 was confirmed by single crystal X-ray analysis. The molecular structure of…

Biomimetic diels–alder cyclizations for the construction of the brevianamide, paraherquamide, sclerotamide, asperparaline and VM55599 ring systems

1998

Abstract A potentially bio-mimetic Diels–Alder cyclization to construct the bicyclo[2.2.2] ring system common to the paraherquamides, marcfortines, sclerotamides, brevianamides, VM55599, and asperparaline is reported. Epi-deoxybrevianamide E (22) is converted into the corresponding lactim ether (23) and then oxidized with DDQ to provide an azadiene (24) which is tautomerized in the presence of base to azadiene 25 which, spontaneously cyclizes to give a 2:1 mixture of cycloadducts 26 and 27. These cycloadducts are each in turn, converted into d , l -C-19-epi-brevianamide A (20) and d , l -brevianamide B (6). The stereochemical implications of the [4+2] cycloaddition is discussed in the conte…

Water-Soluble Palladium Nanoparticles: Click Synthesis and Applications as a Recyclable Catalyst in Suzuki Cross-Couplings in Aqueous Media

2010

A new PEG-tagged material, which was prepared by a threefold copper-catalyzed [3+2] cycloaddition (click chemistry), was found to act as an efficient stabilizer for palladium nanoparticles. The newly formed material proved to be active as a recyclable catalyst in Suzuki coupling; the presence of polyether chains allowed for the catalytic runs to be conducted in aqueous media.

High chemoselectivity of CS dipolarophile in 1,3-dipolar cycloaddition of nitrilimines and 1,2,4-triazepin-5-one derivatives: experimental, theoreti…

2005

Substituted 2,7-dimethyl-3-thioxo-3,4,5,6-tetrahydro-2H-[1,2,4]triazepin-5-one reacts as a dipolarophile with several N-aryl-C-ethoxycarbonylnitrilimines, in equimolar quantities, to give, in all cases, two types of products: diethyl 3-(p-aryl)-2-[N′-(p-aryl)-N′-(2′,7′-dimethyl-5′-oxo-5′,6′-dihydro-2H-[1,2,4]triazepin-3′-yl)-hydrazino]-2,3-dihydro[1,3,4]thiadiazole-2,5-dicarboxylate (3a–3c in 20–25% yield) and ethyl 4-(p-aryl)-5-imino-1,4-dihydro[1,3,4]thiadiazole carboxylate (4a–4c in 45–50% yield). When 1:2 stoichiometry was used, the formation of product 3 (50%) was favoured. The reaction is entirely chemo- and regioselective. The structures of the compounds obtained, where aryl stands f…

Cellulose‑copper as bio-supported recyclable catalyst for the clickable azide-alkyne [3 + 2] cycloaddition reaction in water.

2018

Abstract Naturally-occurring cellulose has been employed as a bio-support macromolecule for the immobilization of either copper(I) or copper(II) ions in order to click azide and alkyne derivatives in water. Under such a click regime, 1,4-disubstitued-1,2,3-triazoles were obtained regioselectively in excellent yields at room temperature. The reaction work-up is simple and the bio-heterogeneous catalyst that has been fully characterized by AAS, SEM, EDX and FT-IR can be easily separated and reused at least five times without any significant decrease in its activity and selectivity, particularly in the case of the very stable CuI-Cellulose.

A combined experimental and theoretical study of the thermal cycloaddition of aryl azides with activated alkenes.

2011

International audience; Reactions were performed from aryl azides on the one hand, and activated alkenes coming from β-dicarbonyl compounds or malonodinitrile on the other hand, either with recourse to conventional heating or to microwave activation, to afford 1-aryl-1H-1,2,3-triazoles. The mechanism and the regioselectivity of the reactions involving β-dicarbonyl compounds have been theoretically studied using DFT methods at the B3LYP/6-31G* level: they are domino processes comprising a tautomeric equilibrium of the β-dicarbonyl compounds with their enol forms, a 1,3-dipolar cycloaddition of the enol forms with the aryl azides (high activation energy), and a dehydration process (lower acti…

Recent advances in copper-based solid heterogeneous catalysts for azide-alkyne cycloaddition reactions

2022

The copper(I)-catalyzed azide−alkyne cycloaddition (CuAAC) reaction is considered to be the most representative ligation process within the context of the “click chemistry” concept. This CuAAC reaction, which yields compounds containing a 1,2,3-triazole core, has become relevant in the construction of biologically complex systems, bioconjugation strategies, and supramolecular and material sciences. Although many CuAAC reactions are performed under homogenous conditions, heterogenous copper-based catalytic systems are gaining exponential interest, relying on the easy removal, recovery, and reusability of catalytically copper species. The present review covers the most recently developed copp…