Search results for "Michael"
showing 10 items of 171 documents
Stereoselective synthesis of carane-based chiral β- and γ-amino acid derivatives via conjugate addition
2015
Abstract Michael addition of dibenzylamine to (−)-tert-butyl isochaminate, prepared in three steps from (−)-perillaldehyde, furnished a carane-based β-amino acid derivative in a highly stereospecific reaction. The resulting amino ester was transformed to the bicyclic amino acid, a promising building block for the synthesis of 1,3-heterocycles and peptidomimetics. The conjugate addition of nitromethane to α,β-unsaturated methyl ester likewise resulted in nitro esters in stereospecific reactions. Catalytic reduction of the nitro group yielded a γ-amino ester. Under acidic conditions, the hydrolysis of the methyl ester resulted in an unexpected aminolactone-type product through rearrangement o…
A new strategy for the synthesis of fluorinated 3,4-dihydropyrimidinones
2009
A new family of 3,4-dihydropyrimidinones (DHPMs) bearing fluorinated substituents at C6 have been prepared from gem-difluorinated nitriles, alkyl 3-butenoates and iso(thio)cyanates. This novel Biginelli-type process relies on the gamma-addition of the ester-derived enolate to fluorinated nitriles. A tandem nucleophilic addition aza-Michael reaction sequence completes the synthetic process. (C) 2009 Elsevier B.V. All rights reserved.
Relationships between kinetic constants and the amino acid composition of enzymes from the yeast Saccharomyces cerevisiae glycolysis pathway
2012
The kinetic models of metabolic pathways represent a system of biochemical reactions in terms of metabolic fluxes and enzyme kinetics. Therefore, the apparent differences of metabolic fluxes might reflect distinctive kinetic characteristics, as well as sequence-dependent properties of the employed enzymes. This study aims to examine possible linkages between kinetic constants and the amino acid (AA) composition (AAC) for enzymes from the yeast Saccharomyces cerevisiae glycolytic pathway. The values of Michaelis-Menten constant (K M), turnover number (k cat), and specificity constant (k sp = k cat/K M) were taken from BRENDA (15, 17, and 16 values, respectively) and protein sequences of nine…
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…
ChemInform Abstract: Microwave-Assisted Tandem Organocatalytic Peptide-Coupling Intramolecular aza-Michael Reaction: α,β-Unsaturated N-Acyl Pyrazoles…
2015
Conjugated N-acyl pyrazoles are successfully employed in the organocatalytic enantioselective intramolecular aza-Michael reaction as ester surrogates.
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 …
Enantioselective Synthesis of Substituted Indoles Through Zirconium(IV)-Catalyzed Friedel–Crafts Alkylation
2012
The chiral complex of ( R )-3,3′-Br 2 -BINOL and zirconium tert -butoxide catalyzes the Friedel–Crafts alkylation of indoles with enones bearing an alkyl or fluorinated group at the β-position to give indoles having a side chain at the C3 position with a tertiary stereogenic center in good yields and with excellent enantioselectivities.
ChemInform Abstract: Mixed Dialkylaluminum Chlorides and Mixed Trimethylorganoaluminates in Chemoselective 1,4-Addition Reactions to Alkylidene Malon…
2010
Mixed alkyl-methyl- and aryl-methylorganoaluminum chlorides 6 were formed by reaction of methylaluminum dichloride with organolithium or Grignard compounds and used for chemoselective 1,4 addition of higher alkyl, aryl, alkenyl and alkinyl groups to alkylidine malonic esters 1 and 2. As an alternative, mixed trimethylorganoaluminates 7 can also be applied for these Michael addition reactions. For conjugate addition of alkenyl groups to alkylidene malonates 1 and 2, alkenyl diisopropylalanes 10 obtained from alkynes and diisopropylaluminum hydride proved the most efficient reagents. Using these novel mixed organoaluminum compounds, β-branched malonic (carboxylic) acid derivatives 3c, 8, 9 an…
ChemInform Abstract: Tandem Asymmetric Michael Reaction-Intramolecular Michael Addition. An Easy Entry to Chiral Fluorinated 1,4-Dihydropyridines.
2010
The sequential treatment of optically active sulfoxide (I) with fluorinated nitriles and alkyl propiolates affords (sulfinylmethyl)dihydropyridines of type (IV) as single diastereomers in most cases.
Organocatalytic enantioselective synthesis of trifluoromethyl-containing tetralin derivatives by sequential (hetero)Michael reaction–intramolecular n…
2017
The enantioselective synthesis of tetralin derivatives bearing a trifluoromethylated all‐carbon quaternary stereocenter has been accomplished through a synthetic sequence comprising an organocatalytic β‐functionalization of ortho‐1‐trifluoromethylvinyl‐(hetero)aromatic conjugated aldehydes followed by the intramolecular nitrone 1,3‐cycloaddition reaction (INCR). Both nitromethane and N‐Cbz‐hydroxylamine were employed as nucleophiles in the initial organocatalytic conjugate addition step, which provided the chiral information required for the subsequent diastereoselective INCR. Although diastereoselectivity was moderate, good yields and enantioselectivities were, in general, obtained. Intere…