Modeling of the glycine tripeptide cyclization in the Ser65Gly/Tyr66Gly mutant of green fluorescent protein

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Structural studies on taurocyamine: 2-[(aminoiminomethyl)-amino]-ethanesulfonic acid

The crystal structure of taurocyamine has been determined by single-crystal diffraction methods. The compound crystallizes in the monoclinic space groupCc witha=5.418(4),b=13.403(9),c=9.533(7) Å,=91.26(4)° andZ=4. The structure was solved by direct methods, and refined by least-squares procedures toR=0.027 (R _w =0.034). The molecule is characterized by statistical distribution of the SO₃H group proton as well of the C=NH proton, suggesting the presence either of different isomers or, in some percentage, of zwitterions in the crystal. An extensive hydrogen-bond system dominates the structure in the crystal state.     

Non-biaryl atropisomers in organocatalysis

A new class of 6'-hydroxy cinchona alkaloids, with a non-biaryl atropisomeric functionalisation at position 5' of the quinoline core can be prepared by an easy amination procedure. These are the first derivatives for which the principle of atropisomerism is engrafted in the classical core of the cinchona alkaloids. The aminated cinchona alkaloids are effective organocatalysts for the Michael addition of beta-keto esters to acrolein and methyl vinyl ketone, in up to 93 % ee (ee=enantiomeric excess), as well as for the asymmetric Friedel-Crafts amination of a variety of 2-naphthols, permitting the preparation of the latter in up to 98 % ee. The aminated 8-amino-2-naphthol itself is the first chiral organocatalyst based on non-biaryl atropisomerism. The two enantiomers of this chiral primary amine can be used for the direct alpha-fluorination of alpha-branched aldehydes. The fluorinated compounds can thereby be accessed in up to 90 % ee.     

New facile tandem route to oxo- and thioxo[1,2,4]triazolo[1,5-a]pyridinium salts

2-Arylsulfanyl- and benzylsulfanylpyridinium N-arylimides (2), easily available from tetrazolo[1,5-b]pyridinium salts (1), participate in 1,3-dipolar cycloaddition with aryl isothiocyanates and aryl isocyanates to result in formation of fused thioxo- and oxo[1,2,4]triazolium salts (5 and 12), respectively. This transformation is interpreted as a regular 1,3-cycloaddition followed by spontaneous elimination of the aryl- or benzylsulfanyl group. Formation of these triazolium salts can be followed--under appropriate reaction conditions--by ring-opening reactions to afford some new triazolyldienes (6). Recognition of the intermediate participation of the thiolate anion along the pathway 1 --> 5 allowed elaboration of a simple procedure to 5 implying a tandem reaction sequence.     

Competitive processes associated to the interaction of a cavitand derivative with caffeic acid

Abstract

The interaction of caffeic acid and a newly synthesised cavitand derivative was investigated by UV–vis and fluorescence spectroscopy in tetrahydrofuran–water matrix. The temperature dependence of the equilibrium constants was determined first, then the thermodynamic parameters were calculated using the van’t Hoff equation. Absorption measurements highlighted entropy-controlled formation of cavitand–caffeic acid complexes with 1:2 stoichiometry. It was proved by fluorescence measurements that caffeic acid dimerisation is followed by the formation of cavitand–caffeic acid complexes with 1:2 stoichiometry. It was also shown that both the caffeic acid dimerisation and the formation of 1:2 complexes are controlled by the entropy gain. PL signal is preferred to use for analytical application in this particular case.     

Synthesis of Vinca Alkaloids and Related Compounds. LXV. Preparation of 7-Methoxytryptamine

7-Methoxytryptamine (6a) was prepared from cheap and easily available starting materials by using the Abramovitch-Shapiro method.