Search results for "EOs"

Exploring the potential of some yeast strains in the stereoselective synthesis of aldol reaction products and its reduced 1,3-dialcohol derivatives

2013

Abstract The behavior of two yeast strains has been studied under different conditions. Both microorganims catalyzed the aldol reaction between activated aldehydes and acetone when a large amount of the latter was present in the reaction medium producing, with moderate stereoselectivity, the aldol product with the R configuration. No reduction of any of the products present in the medium was detected. On the other hand, the carbonyl group of the racemic aldol was reduced to produce chiral 1,3-dialcohol derivatives when water was employed as the only solvent. In this case, the resolution of the racemic starting material was also possible with one of the biocatalysts, and the aldol was recove…

A Novel Approach to Dihydropyrrolones from Iron-Substituted α,β-Unsaturated Imines and Organolithium and Grignard Reagents: Developments, Mechanisms …

2000

Reactions of N-sulfonylimines, derived from Cp(CO)2Fe-substituted (Z)-enals and benzenesulfonamide, with Grignard or organolithium reagents furnish N-sulfonyldihydropyrrolones. When N-sulfinylimines and organometallic reagents are used, unprotected α,β-unsaturated γ-lactams are formed exclusively. Recent mechanistic studies and diastereoselective variations for the synthesis of chiral 5-substituted dihydropyrrolones from iron-substituted azadienes are discussed here.

Relaxation Mechanisms of 5-Azacytosine.

2015

The photophysics and deactivation pathways of the noncanonical 5-azacytosine nucleobase were studied using the CASPT2//CASSCF protocol. One of the most significant differences with respect to the parent molecule cytosine is the presence of a dark (1)(nNπ*) excited state placed energetically below the bright excited state (1)(ππ*) at the Franck-Condon region. The main photoresponse of the system is a presumably efficient radiationless decay back to the original ground state, mediated by two accessible conical intersections involving a population transfer from the (1)(ππ*) and the (1)(nNπ*) states to the ground state. Therefore, a minor contribution of the triplet states in the photophysics o…

Stereoselective Mannich-Type Reaction of an Acyclic Ketimine with a Substituted Chlorotitanium Enolate:  Efficient Approach to d-erythro-α-Trifluorom…

1999

A DFT study of the asymmetric (S)-5-(pyrrolidin-2-yl)-1H-tetrazole catalyzed Michael addition of carbonyl compounds to nitroalkenes

2007

Abstract The role of the ( S )-5-(pyrrolidin-2-yl)-1 H -tetrazole in the asymmetric organocatalyzed Michael addition of carbonyl compounds to nitroalkenes has been studied using DFT methods at the B3LYP/6-31G ∗∗ computational level. For the C–C bond-formation step, several reactive channels have been analyzed. The B3LYP/6-31G ∗∗ results, which are in reasonable agreement with the experiments, allow us to explain the stereoselectivity and the increase of the reactivity achieved by an intramolecular HB between the acid hydrogen of the tetrazole moiety and one oxygen atom of the nitroalkene.

Boron aldol additions with erythrulose derivatives: dependence of stereoselectivity on the type of protecting group

1999

Abstract Boron aldol additions of 1- O -silylated 3,4-di- O -benzyl- and 3,4-di- O -benzoyl- l -erythrulose and achiral aldehydes using dicyclohexylboron chloride have been investigated. The dibenzyl derivative gave syn/syn stereoisomers with high stereoselectivity, whereas the dibenzoyl derivative gave syn/anti stereoisomers. It is believed that, while the dibenzoyl erythrulose gives rise to the E enolate in the presence of dicyclohexylboron chloride, as usually observed with this reagent, only the Z enolate is formed in the case of the dibenzyl derivative.

ChemInform Abstract: Designing P*-Chirogenic Organophosphorus Compounds: From Ligands to Organocatalysts

2015

The interest of organophosphorus compounds bearing chirality on the phosphorus atom has greatly expanded in last decade, due to the development of efficient stereoselective synthetic methods, using...

Using theozymes for designing transition-state analogs for the intramolecular aldol reaction of δ-diketones

2001

Two theozymes for the intramolecular aldol reaction of δ-diketones have been studied using ab initio methods. The presence of both acid/base residues favors several steps of the aldol reaction. The appropriate positioning of these residues can accelerate one of two diastereromeric reaction pathways, the catalyzed aldol reaction being highly stereoselective. Analysis of the geometrical parameters, charge distribution, and the shape of molecular electrostatic potential for the corresponding acid/base catalyzed transition structure allows us to design adequate transition-state analogs to favor a reactive channel of this intramolecular aldol reaction. © 2001 John Wiley & Sons, Inc. Int J Quant …

ChemInform Abstract: Stereoselective Synthesis of Bromopiperidinones and Their Conversion to Annulated Heterocycles.

2010

N-Galactopyranosyland N-glucopyranosyl imines of aliphatic, aromatic and heteroaromatic aldehydes react with 1-methoxy-3-trimethylsilyloxy-1,3-butadiene in a domino Mannich-Michael reaction cascade to give 2-substituted 5,6-dehydro-piperidin-4-ones with high diastereoselectivity. Treatment of these cyclic enaminones with N-bromo-succinimide yields the corresponding 2-substituted 5-bromo-5,6-dehydropiperidinones which react with L-Selectride R © or methylcuprate to afford the saturated bromo-piperidinones with high diastereoselectivity. Condensation reactions of these products with thioamides afford thiazolopiperidines.

Stereoselective synthesis of 2-amino-1-hydroxy-3-phenylpropylphosphonic acid

1996

Abstract A highly stereoselective synthesis of 2-amino-1-hydroxy-3-phenylpropylphosphonic acid was achieved by simple addition of diethyl phosphite to enantiomeric N-blocked phenylalaninals. These compouds exhibit significant herbicidal activity.