Search results for "cycloaddition"

ChemInform Abstract: An Alternative Route to 2H-Naphtho[1,2-b]thiete and Its Cycloaddition Products.

2010

ChemInform Abstract: Synthesis of 5-Substituted 2,3-Dihydrobenzofurans in a One-Pot Oxidation/Cyclization Reaction.

2012

The oxidation of N-protected p-aminophenol derivatives to quinone imides is combined with cycloaddition towards azadiene (II) in a one-pot reaction to give dihydrobenzofuran derivatives in moderate to good yields.

Structural study of ethyl 3-arylcarbamoyl-2,3-diazabicyclo[2.2.1]hept-5-ene-2-carboxylates: conformation and transmission of substituent effects acro…

2001

Nine new ethyl 3-arylcarbamoyl-2,3-diazabicyclo[2.2.1]hept-5-ene-2-carboxylates were prepared by a [4 + 2] cycloaddition and their FTIR, 1H, 13C and 15N NMR spectra were measured and assigned. Single crystals were grown for five compounds and their X-ray data were obtained. The electronic structure and the conformations were calculated by the semi-empirical AM1 method. Using correlations between the spectral, empirical and theoretical structural data, the transmission of substituent effects and the preferential conformation connected with the consecutive double nitrogen inversion and regarding the mutual orientation of NH and CO bonds were investigated. The results are compared with those f…

Experimental and Theoretical Investigations of Structural Trends for Selenium(IV) Imides and Oxides: X-ray Structure of Se3(NAd) 2

2004

The thermal decomposition of Se(NAd)(2) (Ad = 1-adamantyl) in THF was monitored by (77)Se NMR and shown to give the novel cyclic selenium imide Se(3)(NAd)(2) as one of the products. An X-ray structural determination showed that Se(3)(NAd)(2) is a puckered five-membered ring with d(Se-Se) = 2.404(1) A and |d(Se-N)| = 1.873(4) A. On the basis of (77)Se NMR data, other decomposition products include the six-membered ring Se(3)(NAd)(3), and the four-membered rings AdNSe(micro-NAd)(2)SeO and OSe(micro-NAd)(2)SeO. The energies for the cyclodimerization of E(NR)(2) and RNEO (E = S, Se; R = H, Me, (t)Bu, SiMe(3)), and the cycloaddition reactions of RNSeO with E(NR)(2), RNSO(2) with Se(NR)(2), and S…

Synthesis and Stereochemistry of Diepoxynaphthacenes and Tetraepoxyheptacenes

1997

Cycloaddition reactions of 1,4-dihydro-1,4-epoxynaphthalenes (2) and benzo[c]furans (4), generated in situ from the tetracyclone adducts of 2, yield the diepoxynaphthacenes 5 (Schemes 1, 2). Out of 4 possible stereoisomers an exo-exo and an exo-endo geometry (A and C in Scheme 3) can be realized. The ratio A:C varies from pure A to pure C depending on the substituents of 2 and 4. Stereoisomeric heptacenes 7 can be obtained by a twofold cycloaddition of the same type (Scheme 4). Only one π bond of reactive alkynes such as cyclooctyne or acetylenedicarboxylate is capable of an addition to 4 (Schemes 5, 6).

Band-Shaped Structures by Repetitive Cycloaddition Reactions of Benzo[1,2-b:4,5-b′]bisthiete

1997

Benzo[1,2-b:4,5-b′]bisthiete (1) undergoes stepwise thermal opening of the 4-membered rings, thereby generating two highly reactive 8π systems (Scheme 1). In the presence of 1,4-dihydro-1,4-epoxynaphthalenes 2, the dithiaheptacene derivatives 3 are formed, dehydration of which leads to the compounds 4 and 5 (Scheme 2). Repetitive cycloaddition reactions of 1 with the twofold 2π component 11 (Scheme 3) yield the oligomers 15 with statistically bent (and possibly cyclic) structures (Schemes 4 and 5). While 15 and the related oligomers 14 are freely soluble in many organic solvents, the dehydrated systems 16 (Scheme 6) are totally insoluble.

Diversity-Oriented Synthesis of Highly Functionalized Alicycles across Dipolar Cycloaddition/Metathesis Reaction

2021

AbstractThis Account gives an insight into the selective functionalization of some readily available commercial cyclodienes across simple chemical transformations into functionalized small-molecular scaffolds. The syntheses involved selective cycloadditions, followed by ring-opening metathesis (ROM) of the resulting azetidin-2-one derivatives or isoxazoline frameworks and selective cross metathesis (CM) by discrimination of the C=C bonds on the alkenylated heterocycles. The CM protocols have been described when investigated under various conditions with the purpose on exploring chemodifferentiation of the olefin bonds and a study on the access of the corresponding functionalized β-lactam or…

Pauson-Khand reaction of internal dissymmetric trifluoromethyl alkynes. Influence of the alkene on the regioselectivity.

2014

Abstract: The scope of the Pauson-Khand reaction (PKR) of internal trifluoromethyl alkynes, previously described with norbornadiene, is expanded to norbornene and ethylene. A thorough structural analysis of the resulting PK adducts has been carried out to unveil that α-trifluoromethylcyclopentenones are preferred in all cases, independently of the electronic properties of the alkyne. The regioselectivity observed with norbornadiene and ethylene is higher than in the case of norbornene.

Total Synthesis of (-)-Hymenosetin.

2015

The 3-decalinoyltetramic acid (−)-hymenosetin and its N-methyl analogue were prepared in 11 and 8 steps, respectively, from (+)-citronellal using an intramolecular Diels–Alder reaction as the key step. This method represents the first example for the synthesis of a 3-decalinoyltetramic acid with a free NH moiety. The stereochemistry of the title compound, an unnatural diastereomer, and of a decalin building block was studied in detail using circular dichroism spectroscopy in the IR and UV/VIS freqeuncy range. This allowed to determine the absolute configuration of the natural product and to plan the synthetic route.

The tandem Diels-Alder reaction between acetylenedicarboxyaldehyde and N,N'-dipyrrolylmethane. An ab initio study of the molecular mechanisms

1998

Abstract An extensive exploration at RHF/3-21G and RHF/6-31G ∗ levels of the potential energy surface for the tandem cycloaddition of acetylenedicarboxyaldehyde to N,N'-dipyrrolylmethane allows us to characterize the reaction pathways and the associated stationary points. The formation of the pincer and/or domino adducts can be described as a stepwise mechanism. The first step, associated with an intermolecular [4 + 2] cycloaddition, is the rate determining step and an azanorbornadiene intermediate is obtained. The second step is an intramolecular [4 + 2] cycloaddition. The formation of the pincer adduct is the step which kinetically controls the global process, due to the low barrier heigh…