What NMR can do in the biopharmaceutical industry

LBK

Cyclopropanation of Some Alkaloids

New derivatives of natural compounds, galanthamine using in treatment of  Alzheimer’s disease and antitumor dimer alkaloids vinblastine and vincristine were synthesized. In the course of the reaction between galanthamine and diazomethane in the presence of a catalyst, such as palladium(II) acetate or copper(I) bromide, methylene insertion into the aromatic ring was observed instead of the expected cyclopropanation of the carbon-carbon double bond. New vindoline derivatives conjugated with amino acid esters were prepared. In Simmons-Smith reaction vinblastine and vincristine cyclopropanated in the carbon carbon double bond in position 14 and 15 of the vindoline monomer were obtained. New dimer alkaloids showed significant inhibiting effects in several tumor cell lines

Cyclopropanation of carbon-carbon double bonds in ring d of ergot alkaloids

Some ergot alkaloid derivatives containing a double bond in ring D have been reacted with diazomethane/palladium diacetate reagent to result in formation of a fused cyclopropane ring. This procedure proved to be generally applicable for cyclopropanation of Ergot alkaloids

Ergolinvázas alkaloidok és analogonjaik enantioszelektív szintézise = Enantioselective total synthesis of ergot alkaloids and analogues

A (+)-lizergsav és az alpha-ergokriptin totálszintézisének kidolgozása (J. Org. Chem. 2004, Helv. Chim. Acta, 2005, 2 cikk a Magy. Kém. Folyóiratban, 2006; szabadalmi oltalom, 2004). Négy ergolinvázas klavin-alkaloid [(+)-szetoklavin, (+)-izoszetoklavin,és (-)-9,10-dihidroizoszetoklavin és (-)-dihidroszetoklavin] szintézise (+)-8-oxo-ergolénből kiindulva (Heterocycles, 2006). A lizergsav észterek új típusú dimerizációjának megfigyelése és részletes vizsgálata (Heterocycles, 2007). D-nor-ergolinvázas vegyületek szintézise, az eddig egyetlen elő nem állított klavin alkaloid, a (+/-)-cikloklavin totálszintézise (Tetrahedron, 2008). | Total synthesis of (+)-lysergic acid and alpha-ergocryptine (J. Org. Chem., 2004; Helv. Chim. Acta, 2005 and two publications in Magy. Kém. Folyóirat, 2006). Starting from (+)-8-oxo-ergolene synthesis of four clavine alkaloids [(+)-setoclavine, (+)-isosetoclavine, (-)-dihydroisosetoclavine and (-)-dihydrosetoclavine] has been elaborated (Heterocycles, 2006). Observation and detailed study of a new epimerization process of lysergic acid esters. Determination of the mechanism (Heterocycles, 2007). Synthesis of 8-substituted (cyano, alkoxycarbonyl, hydroxymethyl and methyl)-D-norergolenes. Total synthesis of the last so far not synthesized clavine alkaloid, (+/-)-cycloclavine (Tetrahedron, 2008)

Attempted Diels-Alder Reactions on Vindoline Derivatives

The Diels-Alder reaction of vindoline and methyl vinyl ketone resulted in a Friedel-Crafts reaction product. In the reaction between the ortho-quinone derivative of vindoline and N-phenylmaleimide, two anomalous products were obtained, a vindoline dimer, and a condensed vindoline derivative

Synthesis, Fluorescence and NMR Spectroscopic Studies of a Novel Phosphinoxido-18-crown-6 Ether Containing an Anthracene Fluorophore Unit

The synthesis of the (R,R) and (S,S) enantiomers of a new enantiopure monophospha-18-crown-6 ether (1), which contains an anthracene fluorophore unit and methyl groups at its stereogenic centers, was accomplished. The structure of one enantiomer ((S,S)-1) was studied using one-dimensional (1H, 13C{1H}, and 31P{1H}) and two-dimensional NMR spectra. Because (R,R)-1 and (S,S)-1 can act as new fluorescent chemosensors, we examined their enantiomeric differentiation abilities toward the enantiomers of protonated chiral primary amines and amino acid esters (PEA, 1-NEA, PGME, PAME) using UV-Vis and fluorescence spectroscopies. These monophospha-crown ethers showed moderate enantiomeric discrimination abilities