Search results for "Stereom"
showing 10 items of 165 documents
Synthesis of novel isoxazoline-fused cispentacin stereoisomers
2009
Abstract New isoxazoline-fused cispentacins were prepared by the 1,3-dipolar cycloaddition of nitrile oxides to β-amino esters containing a cyclopentene skeleton. This synthetic procedure gave regio- and diastereoisomers of the cispentacins. The synthetic route was extended to the synthesis of these compounds in enantiomerically pure form.
Carbohydrates as chiral templates: asymmetric ugi-synthesis of alpha-amino acids using galactosylamines as the chiral matrices
1988
Abstract In the presence of Lewis acid catalysts O-acetyl- (1) and O-pivaloyl- (2) protected β-D-galactopyranosylamines react with aldehydes, isocyanides and carboxylic acids in Ugi-four-component-condensations to give the corresponding N-galactosyl-amino acid amide derivatives 3,5 in almost quantitative yields. Zinc chloride is the most effective Lewis acid catalyst. At 0°C or even at room temperature the (2R,β-D)-diastereomers of the amino acid derivatives 3,5 are formed with high diastereoselectivity. If the sterically more demanding O-pivaloyl galactosylamine 2 is used at -78°C to -25°C the stereoselectivity often exeeds 20:1 favouring the (2R,β-D) diastereomers 5. After one recrystalli…
Diastereodivergent Synthesis of Fluorinated Cyclic β(3)-Amino Acid Derivatives.
2015
The ability of 2-p-tolylbenzyl carbanions to behave as a source of chiral benzylic nucleophiles has been shown in its reaction with fluorinated imines. The process takes place with high levels of stereocontrol, rendering the corresponding amines as single diastereoisomers. Subsequent cross-metathesis followed by intramolecular aza-Michael reaction makes the synthesis of fluorinated homoproline derivatives bearing three stereogenic centers possible. Furthermore, the selectivity of the cyclization process can easily be tuned up in a diastereodivergent manner simply by changing the reaction conditions.
Experimental and DFT study of the conversion of ephedrine derivatives into oxazolidinones. Double SN2 mechanism against SN1 mechanism
2010
Sulfonation of the N-Boc derivatives of 1,2-aminoalcohols, such as ephedrine, pseudoephedrine, norephedrine, norpseudoephedrine, thiomicamine, and chloramphenicol yields a mixture of the corresponding oxazolidinones with inversion (erythro derivatives) and/or retention of configuration (threo derivatives)at C5. We suggest a competition between two mechanisms: an intramolecular SN2 process initiated by attack of the carbonyl oxygen of the Boc group to the benzylic carbon and the other one through a double SN2 process. In the erythro derivatives the first mechanism is predominant, while in the threo derivatives both mechanisms have similar energy. This hypothesis is supported by theoretical c…
Cyclodextrins in Polymer Synthesis: Enantiodiscrimination in Free-Radical Polymerization of Cyclodextrin-Complexed Racemic N -Methacryloyl-D,L -pheny…
2003
The enantiodiscriminating polymerization of racemic cyclodextrin-complexed N-methacryloylphenylalanine methyl ester is investigated 1 H NMR spectra of the complexes with methylated β-cyclodextrin in D 2 O manifest splittings due to chiral recognition. The different stabilities of the diastereomeric complexes influence the kinetics of the homopolymerization, particularly at 0°C. An enrichment of the residual N-methacryloyl-L-phenylalanine methyl ester of 14% was achieved after 21 h of polymerization.
Stereoselective Synthesis of γ-Fluorinated α-Amino Acids Using 2-Hydroxy-3-pinanone as an Auxiliary
2000
(+)-(S)-2-Amino-4-fluorobutanoic acid (5a) (> 96% ee), its α-methylated derivative (+)-(S)-5b (85% ee), and (−)-(S)-2-amino-4-fluoro-4-pentenoic acid (10) (81% ee) were synthesized by diastereoselective alkylation in the presence of LDA at low temperatures. Alkylation of (+)-(R,R,R)-2-hydroxy-3-pinanone based imines of glycine tert-butyl ester 1a or alanine isopropyl ester 1b with 1-bromo-2-fluoroethane (2) or 3-bromo-2-fluoropropene (7), respectively, followed by stepwise deprotection was used. The selectivity of the alkylation increased by lithium/magnesium exchange or for 1b also by addition of DMPU. Differences in the reactivity of enolate alkylations of enantiomerically pure or racemic…
d-Glucose as a multivalent chiral scaffold for combinatorial chemistry
2002
Due to their high density of functional groups and their availability in a variety of diastereomeric forms, monosaccharides are considered attractive scaffolds for combinatorial chemistry that allow the attachment and defined spatial alignment of up to five different pharmacophoric groups. For their application in combinatorial syntheses on solid phase, a set of selectively removable hydroxy protecting groups in combination with a cleavable anchor is required. Herein, we report on the construction and use of a versatile multivalent glucose building block for parallel synthesis on the solid phase.
Stereoselective synthesis of perillaldehyde-based chiral β-amino acid derivatives through conjugate addition of lithium amides.
2014
The Michael addition of dibenzylamine to (+)-tert-butyl perillate (3) and to (+)-tert-butyl phellandrate (6), derived from (S)-(−)-perillaldehyde (1), resulted in diastereomeric β-amino esters 7A–D in a moderately stereospecific reaction in a ratio of 76:17:6:1. After separation of the diastereoisomers, the major product, cis isomer 7A, was quantitatively isomerized to the minor component, trans-amino ester 7D. All four isomers were transformed to the corresponding β-amino acids 10A–D, which are promising building blocks for the synthesis of β-peptides and 1,3-heterocycles in three steps. The steric effects of the isopropyl group at position 4 and of the α-methyl substituent of (R)-N-benzyl…
Synthesis of nonracemic α-trifluoromethyl α-amino acids from sulfinimines of trifluoropyruvate
2001
We describe a novel and useful method for the synthesis of nonracemic α-trifluoromethyl α-amino acids (α-Tfm-AAs). Key building blocks are the sulfinimines (S)-1a and (S)-1b, prepared by Staudinger reaction from trifluoropyruvate esters and the chiral N-sulfinyl iminophosphorane (S)-8, which were treated with benzyl, allyl, and alkylmagnesium halides. The resulting diastereomeric N-sulfinyl α-Tfm α-amino esters, 12 and 13, were produced with moderate to good stereoselectivity and yields. When alkyl Grignard reagents were used, stereocontrol became progressively higher with increasing steric bulk, while reversed, though poor, stereocontrol was achieved with benzyl/allyl Grignard reagents. An…
Stereoselective synthesis of C-glycosyl compounds via Michael addition of trimethylsilyl enol ethers and enamines to hex-1-enopyran-3-uloses
1987
Abstract The titanium(IV)-catalyzed addition of trimethylsilyl enol ethers to 2,4,6-tri- O -acylhex - 1 - enopyran - 3 - uloses ( 3 and 4 ) gave stereoselectively 3,6 - di - O - acyl - 4 - deoxy - β - d - glycero -hex-3-enopyranosyl-2-ulose derivatives. The formation of the C -glycosyl bond was accompanied by a 2→3 acyl shift, followed by the elimination of the 4-acyloxy substituent. Similarly, the reaction of 1-pyrrolidinocyclohexene with 3 and 4 also led stereoselectively to 2-(2,4,6-tri- O -acyl-β- d - ribo -hexopyranosyl)cyclohexanones. In this Michael addition, among the eight possible diastereomers, only one was formed. The high stereocontrol of both C -glycosyl compound syntheses is …