Search results for "stereochemistry"
showing 10 items of 4831 documents
Quinonoid π-extended tetrathiafulvalenes (TTFs)
2001
Publisher Summary Tetrathiafulvalene (TTF) is a fascinating planar πelectron-donor molecule with a broad range of potential applications. TTF and its derivatives play an important role in the field of organic conductors forming charge-transfer (CT) complexes and radical cation salts (Bechgaard salts) with a huge variety of electron-acceptor molecules and anions in the search for electrically conducting and superconducting materials. The chapter focuses on highly π-extended electron donors with p-quinodimethane structures as interesting precursors of materials with non-conventional properties. The first dimeric examples of π-extended TTF derivatives connected through an oxygen atom are also …
ChemInform Abstract: Concave π-Prismand Hydrocarbon [2.2.2]Cyclophanes and Their Crystalline Ag-Triflate Complexes.
2010
New small concave hydrocarbon cyclophanes were prepared via the well-known HD-2SO2-method. The cyclophanes obtained are isomers of the very well-known [2.2.2]p,p,p-cyclophane, C24H24, a π-prismand efficiently complexing Ag+-ion. X-ray crystal structure determinations showed the bis-sulfide 7 (1,10-dithia[3.3.2]m,p,p-cyclophane) to be helically chiral and that the conformation of the parent hydrocarbon cyclophane 13 ([2.2.2]m,p,p-cyclophane) does not change dramatically upon complexation with the Ag+-ion. The 16- and 17-membered [2.2.2]m,m,p- and [2.2.2]m,p,p-cyclophane (15 and 16) also act as π-prismands and form surprisingly similar crystalline 1:1 Ag-triflate complexes (π-prismates) as th…
Structural characterization in solution of multifunctional nucleotide coordination systems
2000
The interaction in aqueous solution of the cyclophane receptors 2,6,10,13,17,21-hexaaza[22]orthocyclophane (L11) and 2,6,10,13,17,21-hexaaza[22]paracyclophane (L22) with the nucleotides ATP, ADP and AMP has been studied by pH titration and NMR. The obtained results are compared with those previously reported for the analogous meta-substituted receptor 2,6,10,13,17,21-hexaaza[22]metacyclophane (L). All the experimental data support the actuation of these cyclophane molecules as multi-point binders of nucleotides through electrostatic, hydrogen bonding and π-stacking interactions. The combined use of NMR and molecular dynamics permits us to get a rather reliable picture of the way in which th…
Metabolic Inactivation of Reactive Metabolites
1978
ABSTRACT Many compounds which are not electrophilically reactive as such are transformed by mammalian enzymes to reactive metabolites which are, in many cases, responsible for cytotoxic, mutagenic and/or carcinogenic effects of the compounds in question. The essential role of activating systems in this situation has become common knowledge during the last decade. However, many reactive metabolites are also subject to inactivation by mammalian enzymes. This important parameter is frequently not taken into account. Compounds possessing aromatic or olefinic moieties are very widely occurring and activation of these often proceeds via an electrophilically reactive epoxide. This may be transform…
- conformational preference of , -9-oxobicyclo[3.3.1]nonane-2,4-dicarboxylic acid
1985
Abstract The 1 H and 13 C nmr spectra of exo , exo -9-oxobicyclo[3.3.1]nonane-2,4-dicarboxylic acid, 3, in DMSO-d 6 or alkaline D 2 O, clearly show that it exists in a boat - chair -conformation with equatorial carboxyl groups, thus being the first case of boat - chair preference of a bicyclo[3.3.1] nonan-9-one due to the presence of exo , exo -2,4- substituents.
Stereoselective Synthesis of 8,12-Furanoeudesmanes from Santonin. Absolute Stereochemistry of Natural Furanoeudesma-1,3-diene and Tubipofurane.
1996
Ketobutenolide 3, easily obtained from santonin (1), has been transformed into two natural furanoeudesmanes 4 and 5, isolated from Commiphora molmol and Tubipora musica, respectively. trans- And cis-decalin systems were obtained by stereoselective reduction of the C(4)-C(5) double bond in 3 in the following way: hydrogenation of 3 over Pd/C followed by acidic treatment gave the cis isomer 10 as the major product; selective hydrogenation of the C(1)-C(2) double bond with the Wilkinson's catalyst followed by reduction with NaTeH yielded mainly the trans isomer 9. Compounds 9 and 10 were transformed into 4 and 5 in parallel sequences. Optical rotation and CD measurements of the synthetic produ…
Synthesis of peptides with α,β‐dehydroamino acids, III. Debenzyloxycarbonylation and detrifluoroacetylation of dehydroalanine and dehydrophenylalanin…
1985
The removal of amino protecting groups from a series of twelve model Z-3) or TFA-dipeptides of dehydroalanine and (Z)-dehydrophenylalanine was investigated. During this deprotection, peptides with Δ Ala are prone to side reactions to a higher extent than those with Δ Phe. Therefore it is interesting to note that from the Δ Ala peptides, the Z group can be split off in preparative manner with HCO2NH4 in the presence of Pd C (Table 4). Synthese von Peptiden mit α,β-Dehydroaminosauren, III.– Debenzyloxycarbonylierung und Detrifluoracetylierung von Dehydroalanin- und Dehydrophenylalanin-Peptiden An einer Serie von zwolf Z-3) oder TFA-Modellpeptiden mit Dehydroalanin und (Z)-Dehydrophenylalanin …
ChemInform Abstract: Synthesis of α-Fucosyl Glycosides and Disaccharides Using 4- Methoxybenzyl (Mpm) Protected Fucosyl Donors.
2010
The 4-methoxybenzyl (Mpm) group removable by selective oxidation was applied as a nonneighbouring-group-active protection of fucose hydroxy functions in the stereoselective synthesis of α-fucosides of acceptors containing double bonds sensitive to hydrogenation. With this aim, the synthesis of the α-fucosyl chloride (4) carrying the acidsensitive Mpm protection was elaborated.
ChemInform Abstract: Cycloaddition of Benzothiete and Electron-Deficient Nitriles.
2010
The o-quinoid 8π electron system 2, generated by thermal ring opening of benzothiete (1), enters regio-specific [8π + 2π] cycloaddition reactions with electron-deficient nitriles 3a-d, yielding the 4H-1,3-benzothiazines 4a-d. A competitive dimerization of 1 leads to 1,5-dibenzo[b,f]dithiocin (5). Depending on the nitrile further competitive or subsequent reactions (2 + 3b 7b, 2 + 3d 4d 8d) can occur. The cycloadducts 10e and 11e gained from 3e anticipate a primary cleavage of 3e to methylisothiocyanate 9e which reacts at the CN double bond as well as at the CS double bond.
Synthesis of ?-fucosyl glycosides and disaccharides using 4-methoxybenzyl (Mpm) protected fucosyl donors
1992
The 4-methoxybenzyl (Mpm) group removable by selective oxidation was applied as a nonneighbouring-group-active protection of fucose hydroxy functions in the stereoselective synthesis of α-fucosides of acceptors containing double bonds sensitive to hydrogenation. With this aim, the synthesis of the α-fucosyl chloride (4) carrying the acidsensitive Mpm protection was elaborated.