Search results for "Intramolecular force"

A Ferrocenyl Amino Substituted Stannylene as an Intramolecular Fe→Sn Lewis Adduct

2018

Prefolded Synthetic G-Quartets Display Enhanced Bioinspired Properties

2016

International audience; A water-soluble template-assembled synthetic G-quartet (TASQ) based on the use of a macrocyclodecapeptide scaffold was designed to display stable intramolecular folds alone in solution. The preformation of the guanine quartet, demonstrated by NMR and CD investigations, results in enhanced peroxidase-type biocatalytic activities and improved quadruplex-interacting properties. Comparison of its DNAzyme-boosting properties with the ones of previously published TASQ revealed that, nowadays, it is the best DNAzyme-boosting agent.

Intramolecular structural parameters are key modulators of the gel-liquid transition in coarse grained simulations of DPPC and DOPC lipid bilayers

2018

The capability of coarse-grained models based on the MARTINI mapping to reproduce the gel-liquid phase transition in saturated and unsaturated model lipids was investigated. We found that the model is able to reproduce a lower critical temperature for 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) with respect to 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). Nonetheless, the appearance of a gel phase for DOPC is strictly dependent on the intramolecular parameters chosen to model its molecular structure. In particular, we show that the bending angle at the coarse-grained bead corresponding to the unsaturated carbon-carbon bond acts as an order parameter determining the temperature of …

Intramolecular charge transfer and enhanced quadratic optical non-linearities in push pull polyenes

1997

Abstract Push-pull polyenes, which have an electron-donating group (D) and an electron-withdrawing group (A) grafted on opposite ends of a conjugated polyenic chain, are of particular interest as model compounds for long-distance intramolecular charge transfer (ICT), as well as potent non-linear optical chromophores. Several series of push-pull polyenes of increasing length, combining aromatic donor moieties and various acceptor groups, have been prepared and studied. Their linear and non-linear optical properties have been investigated by performing electro-optical absorption measurements (FOAM) and electric-field-induced second-harmonic generation (EFISH) experiments in solution. Each mol…

Diphenoxido‐Bridged Co II and Zn II Complexes of Tripodal N 2 O 2 Ligands: Stabilisation of M II ‐Coordinated Phenoxyl Radical Species

2010

Three new tripodal ligands with an N 2 O 2 donor set, namely 2-tert-butyl-6-({(2-hydroxybenzyl)[2-(2-pyridyl)ethyl]amino}-methyl)-4-methylphenol (H 2 L 1 ), 2-tert-butyl-6-({(2-hydroxybenzyl)[2-(2-pyridyl)ethyl]amino}methyl)-4-methoxy-phenol (H 2 L 2 ) and 2-tert-butyl-6-({[2-(dimethylamino)ethyl]-(2-hydroxybenzyl)amino}methyl)-4-methoxyphenol (H 2 L 3 ) have been synthesised. Treatment of the ligands with Co-(CH 3 CO 2 ) 2 ·4H 2 O or [Zn(H 2 O) 6 ][ClO 4 ] 2 in the presence of Et 3 N provides the corresponding Co II and Zn" complexes of composition [M II 2 (L 1 ) 2 ] [M = Co (1) (single-crystals are a solvate with the composition [Co II 2 (L 1 ) 2 ]·2CHCl 3 , i.e. 1·2CHCl 3 ); M = Zn (2)],…

Derivatisation of Pyrogallarenes

2005

Derivatisation of upper-rim hydroxy groups of pyrogallarenes produced completely acylated and tosylated pyrogallarene derivatives. Mesitylation of pyrogallarene, however, resulted in a regioselective derivatisation of hydroxy groups, i.e. eight OH groups out of 12 were mesitylated. Crystal structures of the synthesised pyrogallarene derivatives indicate that completely substituted pyrogallarenes exist in a distorted crown conformation despite of the lack of stabilising intramolecular hydrogen bonds. In contrast, the partially substituted pyrogallarene adopts a boat conformation and has an open cavity for the inclusion of small guest molecules. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinh…

ChemInform Abstract: A General Overview of the Organocatalytic Intramolecular Aza-Michael Reaction

2015

The organocatalytic intramolecular aza-Michael reaction gives access to enantiomerically enriched nitrogen-containing heterocycles in a very simple manner. Enals, enones, conjugated esters and nitro olefins have been employed as Michael acceptors, while moderate nitrogen nucleophiles such as sulphonamides, carbamates and amides have been shown to be appropriate Michael donors in this type of reaction. Additionally, the process has been performed under both covalent and non-covalent catalysis, with diaryl prolinols, imidazolidinones, thioureas and chiral binol phosphoric acids being the most frequently used catalysts. The level of efficiency reached with this protocol is demonstrated by the …

ChemInform Abstract: Synthesis of 2-Isoxazolines: Enantioselective and Racemic Methods Based on Conjugate Additions of Oximes.

2011

Acidic anilinium salts catalyze the direct formation of racemic 2-isoxazolines from enals and oximes by means of consecutive oxime conjugate-addition and intramolecular oxime-transfer reaction.

Insights into the decomposition pathway of a lutetium alkylamido complex via intramolecular C–H bond activation

2017

Abstract Synthesis, characterization and reaction chemistry of lutetium alkylamido LLu(CH2SiMe3)(NHCPh3) (2), L = 2,5-[Ph2P=N(4-iPrC6H4)]2N(C4H2)–, is reported. Complex 2 undergoes cyclometalation of the NHCPh3 ligand at elevated temperatures to produce the orthometalated complex LLu(κ2−N,C-(NHCPh2(C6H4))) (3) which converts to 0.5 equivalents of bis(amido) LLu(NHCPh3)2 (4) upon heating at 80 °C for 24 h. Reaction of complex 2 with 4-dimethylaminopyridine (DMAP) does not promote alkane elimination nor imido formation. A kinetic analysis of the thermal decomposition of complex 2, supported by deuterium labelling studies and computational analysis (PBE0/def2-TZVP/SDD(Lu)), indicate direct Csp…

Diastereoselective synthesis of antiquorin and related polyoxygenated atisene-type diterpenes

2007

Abstract A diastereoselective approach to polyoxygenated atisene-type diterpenes starting from (S)-(+)-carvone is described. The key steps used in the preparation of the atisene framework are an intramolecular Diels–Alder reaction, an intramolecular diazoketone cyclopropanation, an endocyclic cyclopropane ring cleavage and the regioselective reduction of an allylic bromide by a low-valent chromium species. The synthesis of natural atisanes antiquorin (1), atis-16-ene-3,14-dione (3), atis-16-ene-2,3,14-trione (8) and 3β-hydroxy-atis-16-ene-2,14-dione (9) following this approach is presented. Also described is the synthesis of 18-hydroxy-atis-16-ene-3,14-dione (5), the structure erroneously a…