Search results for "Stereom"
showing 10 items of 165 documents
ChemInform Abstract: Diastereodivergent Synthesis of Fluorinated Cyclic β3-Amino Acid Derivatives.
2016
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: (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).
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.
ChemInform Abstract: Carbohydrates as Chiral Templates: Diastereoselective Synthesis of N- Glycosyl-N-homoallylamines and β-Amino Acids from Imines.
2010
Complexing properties and chirality of carbohydrates were utilized in diastereoselective reactions of 0-pivaloylated N-galactosylimines with allylsilanes and -stannaries. With dyltrimethylsilane in the presence of SnCl4, imines 2 of aromatic and heteroaromatic aldehydes were converted to homdylamines 3, giving ratios of diastereomers higher than 7:1. No addition products derived from α-anomeric aromatic imines were formed. Aliphatic homdylamines 3 were synthesized by using allyltributylstannane in the presence of SnCl4. Both α- and β-anomeric aliphatic imines reacted with the allylstannane. They gave the same ratio of diastereomers and showed the same sense of asymmetric induction.
Structure elucidation of benzopyran-2-ol in solution and in solid state following the reduction of coumarin by DIBAL-H
2001
Lactols are compounds of increasing interest in the synthesis of active pharmaceutical derivatives. Nevertheless, the product obtained by the reduction of the carbonyl group of coumarin has been described only twice, and without definition of its precise chemical structure. Since these studies, doubts have been raised about the existence of a monomeric or dimeric form. Our study has led us to conclude definitely that the single dimeric form exists and to precisely define the spectral properties of the two diastereoisomers.
β-Branched α-Halo Carboxylic Acid Derivatives via Stereoselective 1,4 Addition of Dialkylaluminum Chlorides to α,β-Unsaturated N-Acyloxazolidinones
1997
The stereoselective synthesis of β-branched α-halo carboxylic acids containing two newly formed chiral centers is accomplished by a reaction cascade consisting of the 1,4 addition of dialkylaluminum chlorides to α,β-unsaturated N-acyloxazolidinones and subsequent reaction of the intermediate aluminum enolates with N-halosuccinimide. The most efficient stereocontrol in these tandem processes has been achieved with oxazolidinones derived from glucosamine. Not only aryl substituted but also purely aliphatic β-branched α-halo carboxylic acids can be stereoselectively synthesized by this method. However, the reactions of β-aryl α,β-unsaturated N-acyloxazolidinones show the highest diastereoselec…
Base-Dependent Stereodivergent Intramolecular Aza-Michael Reaction: Asymmetric Synthesis of 1,3-Disubstituted Isoindolines
2013
The nucleophilic addition (A(N)) / intramolecular aza-Michael reaction (IMAMR) process on Ellman's tert-butylsulfinyl imines, bearing a Michael acceptor in the ortho position, is studied. This reaction affords 1,3-disubstituted isoindolines with a wide range of substituents in good yields and diastereoselectivities. Interestingly, careful choice of the base for the aza-Michael step allows either the cis or the trans diastereoisomers to be exclusively obtained. This stereodivergent cyclization has enabled the synthesis of C2-symmetric bisacetate-substituted isoindolines. In addition, bisacetate isoindolines bearing two well-differentiated ester moieties are also noteworthy because they may a…
Asymmetric hydrogenation of an α-unsaturated carboxylic acid catalyzed by intact chiral transition metal carbonyl clusters – diastereomeric control o…
2020
Twenty clusters of the general formula [(μ-H)2Ru3(μ3-S)(CO)7(μ-P–P*)] (P–P* = chiral diphosphine of the ferrocene-based Walphos or Josiphos families) have been synthesised and characterised. The clusters have been tested as catalysts for asymmetric hydrogenation of tiglic acid [trans-2-methyl-2-butenoic acid]. The observed enantioselectivities and conversion rates strongly support catalysis by intact Ru3 clusters. A catalytic mechanism involving an active Ru3 catalyst generated by CO loss from [(μ-H)2Ru3(μ3-S)(CO)7(μ-P–P*)] has been investigated by DFT calculations. peerReviewed
Synthesis of (+)-pechueloic acid and (+)-aciphyllene. Revision of the structure of (+)-aciphyllene
2007
Abstract 1α H ,7α H ,10α H -Guaia-4,11-dien-3-one and its 1β H ,10β H diastereomer, easily obtained from (+)-dihydrocarvone, are good starting materials for the synthesis of natural guaiane derivatives. Allylic oxidation of the 1α H ,10α H isomer gave as main product its 13-hydroxy derivative and a small amount of (+)-7β-hydroxy-1α H ,10α H -guaia-4,11-dien-3-one, whereas the 1β H ,10β H diastereomer afforded selectively the (−)-7α-hydroxy-1β H ,10β H enantiomer in excellent yield. From the 13-hydroxy derivative (+)-pechueloic acid and (+)-methyl pechueloate were synthesized. Deoxygenation at C 3 of the 1β H ,10β H guaiadienone afforded a guaiadiene with the reported structure for aciphylle…
ChemInform Abstract: Synthesis of Novel 1,2,5,6-Tetrahydro-4H-pyrrolo[3,2,1-ij]quinolines via Benzotriazole Methodology.
2010
Abstract Pyrroloquinolines have been synthesized reacting 1-(benzotriazol-1(2)-ylmethyl)indolines with unactivated and electron-rich alkenes in the presence of p-toluenesulfonic acid catalyst. Mixtures of the expected diastereomers were obtained and some of them separated in their respective components. X-Ray diffraction along with two-dimensional NMR experiments was needed to assist the determination for both the structures of the precursors and products.