Search results for "BOND"

1983

The first dissociation constant of oligonuclear phenolic compounds consisting of one nitrophenol unit besides further alkyl phenol units (10 dinuclear, 15 trinuclear, 6 tetranuclear compounds, and 4 nitrophenols as model) was determined spectroscopically in water/methanol (50/50 by vol.) at 25°C. For the ortho-linked title compounds with the nitrophenol unit at the end of the molecule a decrease of pK1 is observed which becomes stronger with increasing chain length. The introduction of bulky groups in ortho-position of the dissociating phenolic unit, as well as at the opposite end of the molecule causes a further decrease of pK1. The lowest value is found for a p-nitrophenol unit in the mid…

Conjugate Alkynylation of Electrophilic Double Bonds. From Regioselectivity to Enantioselectivity

2018

This review surveys the historical efforts addressed toward the development of the conjugate alkynylation reaction. The regio- and enantioselective conjugate alkynylation of electron-deficient double bonds, most commonly unsaturated carbonyl compounds, has been an elusive reaction for a long time. Intensive research during the last decades has resulted in the identification of a number of effective reagents and catalysts to perform this reaction. Non-stereoselective conjugate alkynylation of unsaturated carbonyl compounds was first achieved by using preformed alkynyl organometallics and later with terminal alkynes under catalytic conditions. These methods paved the way for the development o…

Imidazolium functionalized carbon nanotubes for the synthesis of cyclic carbonates: reducing the gap between homogeneous and heterogeneous catalysis

2016

Single walled carbon nanotubes (SWCNTs) were functionalized with imidazolium salts bearing vinyl functionalities. An extremely high loading of active species was achieved through a straightforward one-pot procedure involving self-assembly of the imidazolium moieties followed by radical initiated polymerization of the double bonds. The materials were extensively characterized by transmission electron microscopy, Raman spectroscopy, nitrogen physisorption and combustion chemical analysis. The imidazolium functionalized SWCNTs displayed excellent catalytic activity for the reaction of CO2 and epoxides to produce cyclic carbonates as demonstrated by the excellent turnover numbers (TON). Moreove…

Photoiodocarboxylation of Activated C═C Double Bonds with CO2 and Lithium Iodide

2018

The photolysis at 254 nm of lithium iodide and olefins 1 carrying an electron-withdrawing Z-substituent in CO2-saturated (1 bar) anhydrous acetonitrile at room temperature produces the atom efficient and transition metal-free photoiodocarboxylation of the C═C double bond. The reaction proceeds well for terminal olefins 1 to form the new C-I and C-C σ-bonds at the α and β-positions of the Z-substituent, respectively, and is strongly inhibited by polar protic solvents or additives. The experimental results suggest that the reaction channels through the radical anion [CO2•-] in acetonitrile, yet involves different intermediates in aqueous medium. The stabilizing ion-quadrupole and electron don…

Determination of the absolute configuration of (−)-abietic acidviaits (4R,5R,9R,10R)-7,13-abietadien-18-ylp-bromobenzoate derivative

2006

The absolute configuration of the title bromo derivative of abietic acid, C27H35BrO2, has been determined. The structural analysis confirms the absolute stereochemistry for (−)-abietic acid proposed by Bose & Struck [(1959). Chem. Ind. (London), pp. 1628–1630] on the basis of optical rotatory dispersion measurements. The mol­ecule exhibits a trans anti 6/6/6 tricyclic hydro­carbon skeleton, with the cyclo­hexane ring in the expected chair form and the two cyclo­hexene rings, the double bonds of which are conjugated, in half-chair conformations.

Synthesis of fluorinated piperidine and azepane β-amino acid derivatives

2016

Abstract A convenient and robust stereocontrolled procedure has been developed for the synthesis of novel trifluoromethyl-containing piperidine and azepane β-amino ester stereoisomers. The synthesis started from readily available unsaturated bicyclic β-lactams and was based on oxidative cleavage of the ring C C double bond followed by ring closure of the diformyl intermediates in the presence of 2,2,2-trifluoroethylamine hydrochloride through reductive amination. The synthetic procedure has efficiently been extended towards the synthesis of mono- and difluorinated analogs.

Synthesis of densely functionalized cispentacin derivatives through selective aziridination and aziridine opening reactions: Orthogonally protected d…

2014

A novel substrate-directed synthetic route to a series of highly functionalized, orthogonally protected di- or triaminocyclopentanecarboxylate derivatives with multiple chiral centres from an unsaturated bicyclic β-lactam has been accomplished by applying stereoselective ring C–C double bond aziridination with chloramine-T and phenyltrimethylammonium tribromide, followed by regioselective aziridine opening with different N,O nucleophiles and hydrides. The functionalization strategy was successfully extended for access to enantiomerically pure orthogonally protected triaminocarboxylates.

From linear quaterthiophene to sulflower: A comparative theoretical study

2009

Abstract In this paper, we report a theoretical study of four types of thiophene-based oligomers showing the same number of C C double bonds and very different molecular structures. The comparative study has been performed on the basis of B3LYP/6-31G∗∗ calculations. The way the thiophene rings are linked together has a remarkable influence on the molecular and electronic properties. Linear quaterthiophene and heptathienoacene show similar aromatic structures but a loss of π-conjugation is detected for the latter due to the condensation of thiophene rings. A blue shift of the most intense electronic transition is predicted for fused heptathienoacene compared with non-fused quaterthiophene. C…

Experimental and theoretical studies on corals. I. Toward understanding the origin of color in precious red corals from Raman and IR spectroscopies a…

2009

An attempt to explain the origin of the vivid red color in precious pink and red corals was undertaken. Raman and IR spectroscopies were applied to characterize white, pink and red corals. The position of the Raman signal near 1500 cm −1 of some corals and pearls was associated by several authors with the presence of the mixture of all-trans-polyenic pigments, containing 6 – 16 conjugated C C bonds or β-carotenoids. This hypothesis was examined theoretically by performing extensive B3LYP-DFT calculations of vibrational spectra of the model polyenic compounds. The B3LYP/6-311++G ∗∗ predicted positions of the dominating Raman mode depend on the number of C Cu nits (Cn parameter) and can be ac…

Bonding in the heavy analogue of hydrogen cyanide: the curious case of bridged HPSi.

2010

The bonding of firstand second-row elements differ dramatically. The simplest unsaturated silicon hydrides Si2H2 and Si2H4 exhibit quite unusual geometries [1] compared to the analogous hydrocarbon molecules. For example, the most stable form of Si2H2 is nonplanar with C2v symmetry and two bridging H atoms, in sharp contrast to linear acetylene, HC! CH. Phosphorus and nitrogen share many of the same bonding characteristics, but P prefers single over multiple bonds. For these reasons, it may be difficult to predict the most stable isomeric arrangement, even for a small molecule with a single Por Si atom and especially when it contains both. Silicon–phosphorus bonds are important in materials…