Search results for "proline"

First Evidence of Proline Acting as a Bifunctional Catalyst in the Baylis–Hillman Reaction Between Alkyl Vinyl Ketones and Aryl Aldehydes

2008

Proline in the presence of sodium hydrogen carbonate has been found to be an effective catalyst for the Baylis–Hillman reaction between methyl or ethyl vinyl ketone and aryl aldehydes. Screening of several amine catalysts showed that an ionizable carboxylic function directly linked to the secondary amine catalyst plays an important role in the synthesis of the desired product in good yield. The data obtained has allowed us to suggest, for the first time, that proline, sarcosine, pipecolinic acid and homoproline may act as bifunctional catalysts via a bicyclic enaminolactone species as intermediate. Quantum-mechanical calculations (PM3/COSMO and ab initio 3-21G/COSMO) support this mechanism …

The nucleophilic addition of nitrones to carbonyl compounds: insights on the nature of the mechanism of the l-proline induced asymmetric reaction fro…

2004

Abstract The mechanism of the l -proline induced asymmetric nitrone–aldol reaction of N -methyl- C -ethylnitrone with dimethyl ketomalonate has been studied by using density functional theory at B3LYP/6-31G** level. The reaction was initialized by the addition of l -proline to the nitrone to form an aminal, which by elimination of the hydroxylamine gave a chiral enamine. The nucleophilic addition of this chiral enamine to dimethyl ketomalonate corresponds to stereoselective C–C bond-formation step. Further nucleophilic addition of hydroxylamine to the zwitterionic intermediate formed in the enamine addition gave a second aminal, which by l -proline elimination afforded the corresponding β-h…

Asymmetric Synthesis Using Polymer-Immobilized Proline Derivatives

2011

Characterizing physicochemical, nutritional and quality attributes of wholegrain Oryza sativa L. subjected to high intensity ultrasound-stimulated pr…

2020

Abstract When ultrasonic stimulation is applied to plant seeds it may promote the development of new adaptive characteristics during germination, thus providing an alternative to regulate nutritional and physicochemical attributes of germinated seeds. However, there is rather limited information concerning high-intensity ultrasound (HIU) effects on the germination process of crop seeds as foodstuff. This investigation aimed at examining the effects of a novel processing pattern, which coupled HIU stimulation (28 kHz, 17.83 W cm−2) to a pre-germination stage, on the physicochemical, nutritional and quality changes of wholegrain brown rice (WBR; Oryza sativa L.). Results suggested that HIU st…

Secretion of Protein-bound Hydroxyproline from Moss Callus Cells

1988

Abstract A glycoprotein rich in hydroxyproline was found in wall preparations of callus cells of the moss Physcomitrium pyriforme Brid. It is apparently attached to the non-cellulosic polysaccharides of the wall, and the majority is extractable by boiling the wall fraction or by using a chaotropic salt at room temperature. A pulse-chase technique was used to study the transport of this protein to the wall. Cytochalasin B seems to inhibit its secretion from the callus cells. Some of this wall-associated protein is probably secreted from the cells into the medium. Electron microscopic evidence shows vesicular activity in the cytoplasm and secretion and incorporation into the wall layers (not …

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.

ChemInform Abstract: Asymmetric Synthesis Using Polymer-Immobilized Proline Derivatives

2012

Studies on the biosynthesis of paraherquamide. Construction of the amino acid framework

2001

Abstract It has been previously established in this laboratory that the β-methyl-β-hydroxyproline moiety of the potent anthelmintic agent paraherquamide A, is biosynthetically derived from l -isoleucine. The downstream events from l -Ile to paraherquamide A have now been investigated. The synthesis of [1- 13 C]-labeled l -β-methylproline is described by means of a Hoffman–Loeffler–Freytag reaction sequence from [1- 13 C]- l -Ile. This amino acid is shown to be a direct biosynthetic precursor to paraherquamide A by feeding and incorporation experiments in growing cultures of Penicillium fellutanum . Three tryptophan-containing dipeptides of l -β-methylproline have been constructed: [ 13 C 2 …

Studies on the Content of Free Amino Acids in Needles of Undamaged and Damaged Spruce Trees at a Natural Habitat

1990

Summary Measurements of the amino acids in needles of undamaged and damaged 90-year-old spruce trees ( Picea abies ) showed different patterns. During the summer months a reduction in total amino acid content of about 60 % was found. In autumn the content of total amino acids rose again. The courses of the single amino acids behave similarly to that of the total amino acids. Quantitatively, the main amino acids were GLU, ASP and GLN with about 37 %, 21 % and 10 %, respectively, followed by PRO, ALA and SER with about 3–4 % each. In the needles of healthy trees large variations in ARG content could be observed. These variations correlate neither with the damage degree of the trees nor with t…

ChemInform Abstract: (S)-Proline Benzyl Ester as Chiral Auxiliary in Lewis Acid-Catalyzed Asymmetric Diels-Alder Reactions.

1989

Asymmetric Diels-Alder reaction of cyclopentadiene (I) with (S)-proline benzyl ester (II) yields a mixture of the diastereomeric cycloadducts (R)-(III) and (S)-(IV).