Asymmetric synthesis of N-aryl substituted chiral 1,4-aminoalcohol derivatives and applications in various asymmetric transformation reactions

Download

index.pdf

Date

2007

Author

Odabaş, Serhat

Metadata

Show full item record

Item Usage Stats

333
views

122
downloads

The asymmetric synthesis of N-aryl substituted chiral 1,4-aminoalcohols and their applications in asymmetric borane reduction and enantioselective diethylzinc addition to benzaldehyde reactions were performed starting from meso-anhydride 51 that is the cycloadduct of cyclopentadiene and maleic anhydride. The desymmetrization of meso-anhydride 51 was achieved by using quinine or quinidine with very high enantiomeric excess value (up to 98% ee) and with high chemical yield. The quinine-mediated desymmetrization of meso-anhydride 51 with methanol gave (2S,3R)-(-)-cis-monoester 52. The hemiester was subjected to chemoselective amidation with various types of N-aryl substituted amines and then, it was treated with LAH and followed by hydrogenation in the presence of palladium catalyst to get the chiral 1,4-amino alcohols. The catalytic effectiveness of these chiral 1,4-amino alcohol ligands, (2S,3R)-60, (2S,3R)-61, (2S,3R)-62 and (2S,3R)-63 were examined in asymmetric borane reduction and enantioselective diethylzinc addition to benzaldehyde reactions.

Subject Keywords

Chemistry, Organic

URI

http://etd.lib.metu.edu.tr/upload/12608489/index.pdf
https://hdl.handle.net/11511/16956

Collections

Graduate School of Natural and Applied Sciences, Thesis

Suggestions

OpenMETU
Core

Asymmetric synthesis of norbornene based 1,4-Aminoalcohol derivatives and applications in asymmetric diethylzinc reactions Erdem, Mine; Tanyeli, Cihangir; Department of Chemistry (2007) The asymmetric synthesis of chiral norbornene based 1,4-aminoalcohols and their applications in asymmetric diethylzinc addition reactions was perfomed starting from meso-anhydride 50. The desymmetrization of this meso-anhydride 50 was done by the usage of quinine or quinidine cinchona alkaloids with very high enantiomeric excess values (up to 98% ee) and chemical yields. The Quinidine-mediated desymmetrization of meso-anhydride 50 with methanol gave (2R,3S)-(+)-cis-monoester 51. The amination of this result...
Asymmetric synthesis of norbornene based 1,4-amino alcohol derivatives and applications in asymmetric transformations Sünbül, Murat; Tanyeli, Cihangir; Department of Chemistry (2005) The asymmetric synthesis of cis-1,4-aminoalcohols with norbornene backbone was performed starting with simple and cheap anhydride 30. Quinine-mediated desymmetrization of anhydride 30 with methanol resulted in (2S,3R)-(-)-cis-hemiester 31 (98% e.e.). Chemoselective amination with HMPTA and NH4OH followed by LAH reduction afforded (2S,3R)-(+)-36 and (2S,3R)-(-)-37, respectively. The amidoester (2S,3R)-(-)-32 was transformed into chiral ligand (2S,3R)-(-)-35 with Grignard reaction followed by LAH reduction. T...
Naphthazarin-Polycyclic Conjugated Hydrocarbons and Iptycenes Dengiz, Çağatay; GUTIERREZ, Gregory D.; SWAGER, Timothy M. (American Chemical Society (ACS), 2017-07-21) The synthesis of a set of naphthazarin-containing polycyclic conjugated hydrocarbons is described herein. Sequential Diels-Alder reactions on a tautomerized naphthazarin core were employed to access the final conjugated systems. Complete conjugation across the backbone can be achieved through complexation with BF2, as observed by (HNMR)-H-1 analysis and UV/vis spectroscopy. Precise synthetic control over the degree of oxidation of naphthazarin quinone Diels-Alder adduct 10 is additionally demonstrated and e...
DFT calculations of pentalenoquinones: towards the interception of 2-bromopentalene-1,5-dione Atalar, Taner; Algi, Fatih; Balcı, Metin (ARKAT USA, Inc., 2008-01-01) To reveal the stability and the aromatic character of pentalenoquinones (PQs) 1-4 and the corresponding bromo derivatives (Br-PQs) 6-9, DFT calculations (B3LYP/6-311+G(d,p)) concerning the geometry optimization, total energy and nucleus independent chemical shift (NICS) values were performed. It was found that all of the compounds have planar geometry. As the energy difference between HOMO-LUMO energy levels (Delta epsilon=epsilon(LUMO) - epsilon(HOMO)) and total energies were considered for the pentalene f...
Chemoenzymatic synthesis of chiral hydroxymethyl cycloalkenols Şenocak, Deniz; Demir, Ayhan Sıtkı; Department of Chemistry (2004) Chiral cyclic alkenols with hydroxymethyl functionality are important structural units in many biologically active natural compouds such as prostaglandins, sesquiterpene antiviral agents, pentenomycins, xanthocidin, sarkomycin, etc. 1,3-cycloalkanediones are converted into bicyclic polyoxo derivatives with formaldehyde and trioxane in the presence of Lewis acid. Selective oxidation of the bicyclic compounds by using manganese(III)acetate followed by enzyme-catalyzed kinetic resolution afforded chiral bicycl...

Citation Formats

S. Odabaş, “Asymmetric synthesis of N-aryl substituted chiral 1,4-aminoalcohol derivatives and applications in various asymmetric transformation reactions,” M.S. - Master of Science, Middle East Technical University, 2007.