Luisa Fernanda Avila Carrillo - Academia.edu (original) (raw)
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Papers by Luisa Fernanda Avila Carrillo
Chemistry (Weinheim an der Bergstrasse, Germany), Jan 21, 2018
In this work, carboxylic acids, which are typically regarded as poor nucleophiles, are demonstrat... more In this work, carboxylic acids, which are typically regarded as poor nucleophiles, are demonstrated to be competent reagents to promote the ring-opening of formylcyclopropanes after activation of the latter through iminium ion formation. Under optimized reaction conditions, a variety of γ-acyloxy-substituted aldehydes can be obtained in high yields and enantioselectivities through the desymmetrization of substituted meso-formylcyclopropanes in the presence of a chiral secondary amine as catalyst.
Angewandte Chemie (International ed. in English), Jan 2, 2018
Racemic cyclopropyl ketones undergo enantioselective rearrangement to deliver the corresponding d... more Racemic cyclopropyl ketones undergo enantioselective rearrangement to deliver the corresponding dihydrofurans in the presence of a chiral phosphoric acid as the catalyst. The reaction involves activation of the donor-acceptor cyclopropane substrate by the chiral Brønsted acid catalyst to promote the ring-opening event, thus generating a carbocationic intermediate that subsequently undergoes cyclization. Computational studies and control experiments support this mechanistic pathway.
Chemistry (Weinheim an der Bergstrasse, Germany), Jan 24, 2017
The reaction of nitrones with enals through iminium activation can be modulated by using cooperat... more The reaction of nitrones with enals through iminium activation can be modulated by using cooperative hydrogen-bonding catalysis to induce the participation of a nitrone ylide (C-N-C) instead of the classical C-N-O dipole. As a consequence, N-hydroxypyrrolidines are obtained, rather than the expected isoxazolidines. The reaction proceeds smoothly and high enantioselectivities are observed in all cases. By using the appropriate substrate, polysubstituted pyrrolidines incorporating quaternary stereocenters can be efficiently prepared.
Angewandte Chemie (International ed. in English), Jan 3, 2017
BINOL-based N-trifluoromethanesulfonyl phosphoramides have been used to catalyze the enantioselec... more BINOL-based N-trifluoromethanesulfonyl phosphoramides have been used to catalyze the enantioselective (4+3) cycloaddition between furans and oxyallyl cations, the latter being generated in situ by oxidation of allenamides. In this methodology, the chiral organic phosphoramide counteranion is proposed to engage in the activation of the oxyallyl cation intermediate through cooperative H-bonding and ion pairing interactions enabling an efficient chirality transfer that provide the final adducts with high diastereo- and enantioselectivities. Remarkably, the reaction shows a wide substrate scope, performing well with a variety of substituted allenamides and furans.
Chemistry - A European Journal, 2015
Chemistry - A European Journal, 2014
![Research paper thumbnail of ChemInform Abstract: Stereocontrolled Synthesis of 2-Aryl Tetralones. Application in the Synthesis of B/C Hexahydrobenzo[c]phenanthridine Alkaloids](https://attachments.academia-assets.com/88063222/thumbnails/1.jpg)
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Synthesis, 2011
We have carried out the stereoselective synthesis of (-)-β-conhydrineand (+)-α-conhydrine, two bi... more We have carried out the stereoselective synthesis of (-)-β-conhydrineand (+)-α-conhydrine, two bioactive α-hydroxyalkyl-substitutedpiperidines, using the commercially available and inexpensive aminoalcohol ( S, S)-(+)-pseudoephedrineas chiral auxiliary. The key step of this synthesis relies on newmethodology previously developed in our group, consisting of thechemo- and dia-stereoselective addition of Grignard reagentsacross the C=N bond of α-iminoglyoxylamides derivedfrom ( S, S)-(+)-pseudoephedrinefollowed by the selective monoaddition of organolithium reagents- tothe carbamoyl group, leading to the formation of enantioenriched α-aminoketones.
Synthesis, 2010
We have developed a very efficient procedure for carrying out the cyclopropanation reaction of α,... more We have developed a very efficient procedure for carrying out the cyclopropanation reaction of α,β-unsaturated aldehydes with diethyl bromomalonate using an O-TMS-diarylprolinol as a catalyst. We have found that the use of water as reaction medium results in a remarkable beneficial effect on the reaction, allowing it to be performed without the need to incorporate one equivalent of an external base, which is the case in other similar methodologies reported. In addition, several new chiral pyrrolidines have been prepared that have potential for improved ability as a catalyst for this transformation in aqueous media. In this context, a modified 0-TMS-diarylprolinol incorporating a hydrophobic alkyl side chain has been identified as a promising catalyst for this reaction.
Letters in Organic Chemistry, 2004
Journal of the American Chemical Society, 2012
Donor-acceptor monosubstituted hydrazones participate as suitable reagents able to undergo an ena... more Donor-acceptor monosubstituted hydrazones participate as suitable reagents able to undergo an enantioselective formal diaza-ene reaction with α,β-unsaturated aldehydes under chiral secondary amine catalysis. This constitutes a new approach for the enantioselective conjugate addition of hydrazones to enals under metal-free conditions and leads to the formation of γ-hydrazono carboxylic acids after oxidation/[1,3]-H shift. The methodology is also useful for the synthesis of enantioenriched β-substituted α-keto-1,5-diesters by using the hydrazone moiety as a masked carbonyl group.
The Journal of Organic Chemistry, 1999
A highly enantioselective method for the synthesis of 4-alkyl substituted 1,2,3,4-tetrahydroisoqu... more A highly enantioselective method for the synthesis of 4-alkyl substituted 1,2,3,4-tetrahydroisoquinolines is reported. The key step relies on the asymmetric synthesis of alpha-alkylarylacetic acids by alkylation of their corresponding amides employing (S,S)-(+)-pseudoephedrine as chiral inductor. Subsequent Friedel-Crafts acylation, stereocontrolled reductive amination and Pictet-Spengler cyclization affords the title compounds in excellent yields and enantioselectivities.
The Journal of Organic Chemistry, 2005
Chemistry (Weinheim an der Bergstrasse, Germany), Jan 21, 2018
In this work, carboxylic acids, which are typically regarded as poor nucleophiles, are demonstrat... more In this work, carboxylic acids, which are typically regarded as poor nucleophiles, are demonstrated to be competent reagents to promote the ring-opening of formylcyclopropanes after activation of the latter through iminium ion formation. Under optimized reaction conditions, a variety of γ-acyloxy-substituted aldehydes can be obtained in high yields and enantioselectivities through the desymmetrization of substituted meso-formylcyclopropanes in the presence of a chiral secondary amine as catalyst.
Angewandte Chemie (International ed. in English), Jan 2, 2018
Racemic cyclopropyl ketones undergo enantioselective rearrangement to deliver the corresponding d... more Racemic cyclopropyl ketones undergo enantioselective rearrangement to deliver the corresponding dihydrofurans in the presence of a chiral phosphoric acid as the catalyst. The reaction involves activation of the donor-acceptor cyclopropane substrate by the chiral Brønsted acid catalyst to promote the ring-opening event, thus generating a carbocationic intermediate that subsequently undergoes cyclization. Computational studies and control experiments support this mechanistic pathway.
Chemistry (Weinheim an der Bergstrasse, Germany), Jan 24, 2017
The reaction of nitrones with enals through iminium activation can be modulated by using cooperat... more The reaction of nitrones with enals through iminium activation can be modulated by using cooperative hydrogen-bonding catalysis to induce the participation of a nitrone ylide (C-N-C) instead of the classical C-N-O dipole. As a consequence, N-hydroxypyrrolidines are obtained, rather than the expected isoxazolidines. The reaction proceeds smoothly and high enantioselectivities are observed in all cases. By using the appropriate substrate, polysubstituted pyrrolidines incorporating quaternary stereocenters can be efficiently prepared.
Angewandte Chemie (International ed. in English), Jan 3, 2017
BINOL-based N-trifluoromethanesulfonyl phosphoramides have been used to catalyze the enantioselec... more BINOL-based N-trifluoromethanesulfonyl phosphoramides have been used to catalyze the enantioselective (4+3) cycloaddition between furans and oxyallyl cations, the latter being generated in situ by oxidation of allenamides. In this methodology, the chiral organic phosphoramide counteranion is proposed to engage in the activation of the oxyallyl cation intermediate through cooperative H-bonding and ion pairing interactions enabling an efficient chirality transfer that provide the final adducts with high diastereo- and enantioselectivities. Remarkably, the reaction shows a wide substrate scope, performing well with a variety of substituted allenamides and furans.
Chemistry - A European Journal, 2015
Chemistry - A European Journal, 2014
Synthesis, 2011
We have carried out the stereoselective synthesis of (-)-β-conhydrineand (+)-α-conhydrine, two bi... more We have carried out the stereoselective synthesis of (-)-β-conhydrineand (+)-α-conhydrine, two bioactive α-hydroxyalkyl-substitutedpiperidines, using the commercially available and inexpensive aminoalcohol ( S, S)-(+)-pseudoephedrineas chiral auxiliary. The key step of this synthesis relies on newmethodology previously developed in our group, consisting of thechemo- and dia-stereoselective addition of Grignard reagentsacross the C=N bond of α-iminoglyoxylamides derivedfrom ( S, S)-(+)-pseudoephedrinefollowed by the selective monoaddition of organolithium reagents- tothe carbamoyl group, leading to the formation of enantioenriched α-aminoketones.
Synthesis, 2010
We have developed a very efficient procedure for carrying out the cyclopropanation reaction of α,... more We have developed a very efficient procedure for carrying out the cyclopropanation reaction of α,β-unsaturated aldehydes with diethyl bromomalonate using an O-TMS-diarylprolinol as a catalyst. We have found that the use of water as reaction medium results in a remarkable beneficial effect on the reaction, allowing it to be performed without the need to incorporate one equivalent of an external base, which is the case in other similar methodologies reported. In addition, several new chiral pyrrolidines have been prepared that have potential for improved ability as a catalyst for this transformation in aqueous media. In this context, a modified 0-TMS-diarylprolinol incorporating a hydrophobic alkyl side chain has been identified as a promising catalyst for this reaction.
Letters in Organic Chemistry, 2004
Journal of the American Chemical Society, 2012
Donor-acceptor monosubstituted hydrazones participate as suitable reagents able to undergo an ena... more Donor-acceptor monosubstituted hydrazones participate as suitable reagents able to undergo an enantioselective formal diaza-ene reaction with α,β-unsaturated aldehydes under chiral secondary amine catalysis. This constitutes a new approach for the enantioselective conjugate addition of hydrazones to enals under metal-free conditions and leads to the formation of γ-hydrazono carboxylic acids after oxidation/[1,3]-H shift. The methodology is also useful for the synthesis of enantioenriched β-substituted α-keto-1,5-diesters by using the hydrazone moiety as a masked carbonyl group.
The Journal of Organic Chemistry, 1999
A highly enantioselective method for the synthesis of 4-alkyl substituted 1,2,3,4-tetrahydroisoqu... more A highly enantioselective method for the synthesis of 4-alkyl substituted 1,2,3,4-tetrahydroisoquinolines is reported. The key step relies on the asymmetric synthesis of alpha-alkylarylacetic acids by alkylation of their corresponding amides employing (S,S)-(+)-pseudoephedrine as chiral inductor. Subsequent Friedel-Crafts acylation, stereocontrolled reductive amination and Pictet-Spengler cyclization affords the title compounds in excellent yields and enantioselectivities.
The Journal of Organic Chemistry, 2005