Search results for "CHIRAL AUXILIARY"
showing 10 items of 28 documents
Tetrazola hemiamināls kā hirāla palīggrupa
2017
Tetrazola hemiamināls kā hirāla palīggrupa. Sējējs M., zinātniskais vadītājs Prof., Dr. chem. Sūna E., konsultēja MSc. chem., Kinēns A. Maģistra darbs uzrakstīts latviešu valodā, tā apjoms 58 lapaspuses. Darbs satur 56 attēlus, 5 tabulas. Maģistra darbs veltīts terazolu hemiaminālu hirālās palīggrupas iegūšanai un pielietojumam diastereoselektīvajā sintēzē. Izstrādātās hirālās palīggrupas efektivitāte demonstrēta, ar augstu diastereoselektivitāti veicot karbonskābju α-pozīcijas fluorēšanas un nitrozo-aldola reakcijas. Darba rezultātā izstrādāts tetrazola hemiamināla hirālās palīggrupas stereoindukcijas modelis. Demonstrēta hirālās palīggrupas šķelšana maigos reakcijas apstākļos. Tetrazola h…
A Supramolecular Chiral Auxiliary Approach: “Remote Control ”of Stereochemistry at a Hierarchically Assembled Dimeric Helicate
2016
Dimeric hierarchically-assembled titanium(IV) helicates are in solvent-dependent equilibrium with the corresponding monomers. Statistically formed mixtures of such complexes bearing chiral stereocontrolling ligands and achiral diene-substituted ligands show high diastereoselectivity and reasonable enantioselectivity in the Diels-Alder reaction with maleimides if the reaction proceeds with the dimer but not with the monomer. Thus, solvent dependent switching between the monomer and dimer enables on/off switching of the enantioselectivity.
Solution-, solid-phase, and fluorous synthesis of beta,beta-difluorinated cyclic quaternary alpha-amino acid derivatives: a comparative study.
2008
The diastereoselective synthesis of cyclic beta,beta-difluorinated alpha-amino acid derivatives bearing a quaternary stereocenter is described. The process relies on the chemo- and diastereoselective addition of allylic organometallic reagents to fluorinated alpha-imino esters and a subsequent ring-closing metathesis reaction (RCM). Complete selectivity in the nucleophilic addition was achieved with (R)-phenylglycinol methyl ether as a chiral auxiliary. The resulting amino acids were introduced into peptide chains, which could facilitate the preparation of potentially bioactive dipeptide derivatives. In addition, the solution synthesis of these cyclic fluorinated alpha-amino acids was succe…
Bubble fractionation of enantiomers from solution using molecularly imprinted polymers as collectors.
1998
Adsorptive bubble separation methods have been used to enrich components from both heterogeneous and homogeneous solutions. These methods are particularly effective for processing large solution volumes at low cost. Previous work demonstrated that chiral, surface-active collectors could be used to enrich enantiomers from homogeneous solution in a foam fractionation process. In a significant extension of this work, the use of highly selective molecularly imprinted polymers (MIPs) and heterogeneous solutions for the bubble flotation of enantiomers was evaluated. The high selectivity and ease of recycling of the MIP make this a potentially powerful approach for process-scale separations from l…
Cross-Metathesis Reactions as an Efficient Tool in the Synthesis of Fluorinated Cyclic β-Amino Acids
2009
The synthesis of enantiomerically pure, cyclic, gamma,gamma-difluorinated beta-amino acids with various ring sizes has been carried out with a cross-metathesis (CM) reaction being one of the key steps, followed by a Dieckmann-type condensation to bring about the cyclization. Subsequent catalytic hydrogenation under microwave irradiation with (-)-8-phenylmenthol as a chiral auxiliary led to the successful chemo- and diastereoselective chemical reduction of the resulting cyclic beta-enamino esters. The efficiency and scope of the CM reaction with different types of fluorinated imidoyl chlorides and unsaturated esters has also been studied in order to determine the optimal reaction conditions …
New Strategy for the Stereoselective Synthesis of Fluorinated β-Amino Acids
2002
Racemic and chiral nonracemic alpha-substituted and alpha-unsubstituted beta-fluoroalkyl beta-amino acid derivatives 6 and 9 have been synthesized in two steps starting from fluorinated imidoyl chlorides 1 and ester enolates. This approach is based on the chemical reduction of previously obtained gamma-fluorinated beta-enamino esters 4 by using ZnI(2)/NaBH(4) in a nonchelated aprotic medium (dry CH(2)Cl(2)) as the reducing agent. A metal-chelated six-membered model has been suggested to explain the stereochemical outcome of the reduction reaction. The process takes place with high yields and with moderate to good diastereoselectivity. The best results related to diastereoselective reduction…
Synthesis of a New Fluorinated Oxazolidinone and Its Reactivity as a Chiral Auxiliary in Aldol Reactions.
2007
A new enantiomerically pure fluorinated oxazolidinone has been prepared from a fluorinated imidoyl chloride and an optically pure sulfoxide. The diastereoselective reduction of the β-iminosulfoxide thus formed followed by elimination of the sulfoxide and cyclization of the created aminoalcohol furnishes the desired product. The fluorinated oxazolidinone was subsequently used as a chiral auxiliary in Aldol reactions. We also found that the selective formation of the syn-Evans and syn-non-Evans diastereoisomer can be controlled by adjusting the Lewis acid/base ratio.
Stereoselective synthesis of benzomorphan derivatives with perpivaloylated galactose as the chiral auxiliary.
2006
Synthesis and Derivatization of Substituted (R)- and (S)-C-Allylglycines
2004
Various (R)- and (S)-C-allylglycine derivatives were synthesized by means of an auxiliary controlled diastereoselective aza-Claisen rearrangement. Starting from (S)-configured auxiliaries derived from optically active proline, an aza-Claisen rearrangement enabled us to synthesize α(R)-configured γ,δ-unsaturated amides. Since (R)-allylglycine derivatives could be directly generated by reacting N-allylproline derivatives and various protected glycine fluorides, the corresponding (S)-enantiomers were built-up via an initial α-chloroacetyl chloride rearrangement and a subsequent chloride azide substitution with complete inversion of the configuration. High diastereoselectivities were obtained (…
Asymmetric Synthesis of New β,β-Difluorinated Cyclic Quaternary α-Amino Acid Derivatives
2006
The synthesis of new beta,beta-difluorinated cyclic quaternary alpha-amino acid derivatives 1 in which a ring-closing metathesis reaction (RCM) constitutes the key step is described. The approach employs imidoyl chlorides 3 as fluorinated building blocks, and the overall process involves the stereoselective creation of a quaternary stereocenter. Complete selectivity was achieved when (R)-phenylglycinol methyl ether was used as chiral auxiliary, allowing for the preparation of new six-membered cyclic fluorinated alpha-amino acids as single enantiomers.