Mario Ordóñez - Academia.edu (original) (raw)
Papers by Mario Ordóñez
Tetrahedron-asymmetry, 2003
An efficient synthesis of both enantiomers of g-amino-b-hydroxypropylphosphonic acid, an analogue... more An efficient synthesis of both enantiomers of g-amino-b-hydroxypropylphosphonic acid, an analogue of GABOB, has been achieved for the first time starting from glycine, through the resolution of dimethyl (±)-3-(N,N-dibenzylamino)-2-hydroxypropylphosphonate 7 with (S)-O-methylmandelic acid.
Tetrahedron-asymmetry, 2004
The reduction of dimethyl 3-N,N-di(a-methylbenzyl)amino-2-ketophosphonates 9 with catecholborane ... more The reduction of dimethyl 3-N,N-di(a-methylbenzyl)amino-2-ketophosphonates 9 with catecholborane at À78°C in presence of LiClO 4 , gave c-amino-b-hydroxyphosphonates 10 and 11 in good yield and with excellent diastereoselectivity. This procedure represents an example of highly diastereoselective 1,4-induction. The hydrolysis and hydrogenation of 10 and 11 afforded the (R)-and (S)-c-amino-b-hydroxypropylphosphonic acid (GABOB P ), respectively.
Tetrahedron-asymmetry, 2010
Tetrahedron-asymmetry, 2008
Reduction of b-keto-diphenylphosphine oxide (S)-4 derived from (S)-mandelic acid with NaBH 4 in m... more Reduction of b-keto-diphenylphosphine oxide (S)-4 derived from (S)-mandelic acid with NaBH 4 in methanol at À78°C gave the anti-3-diphenylphosphinoyl-1,2-diol 6, whereas the reduction of (S)-4 with Zn(BH 4 ) 2 in THF at À78°C afforded the syn-1,2-diol 5, both in high yield and excellent diastereoselectivity. This procedure represents a new approach to the diastereoselective synthesis of diphenylphosphinoyl diols and an example of highly diastereoselective 1,2-induction. A theoretical model to explain the direction and degree of asymmetric induction is proposed.
A new efficient and practical synthesis of syn-and antib,g-dihydroxyphosphonates 1 and 2 was deve... more A new efficient and practical synthesis of syn-and antib,g-dihydroxyphosphonates 1 and 2 was developed in high diastereoselectivity via reduction of b-ketophosphonates readily obtained from (S)-mandelic acid. An example of "diastereoselective 1,2-induction" is showed and a mechanistic model to explain the stereochemical outcome is proposed. Assignment of the configuration at the new stereogenic centers was achieved by 1 H NMR spectral data of their corresponding acetonides.
Tetrahedron-asymmetry, 2002
The reduction of g-N,N-dibenzylamino-b-ketophosphonates 4 derived from readily available (S)-trib... more The reduction of g-N,N-dibenzylamino-b-ketophosphonates 4 derived from readily available (S)-tribenzylated amino acids was achieved with catecholborane at -20°C affording g-amino-b-hydroxyphosphonates 5 in high diastereoselectivity and good chemical yield. These reactions provide a new entry to enantiomerically pure g-amino-b-hydroxyphosphonates.
Tetrahedron-asymmetry, 2009
The most recent papers describing the stereoselective synthesis of cyclic quaternary α-amino acid... more The most recent papers describing the stereoselective synthesis of cyclic quaternary α-amino acids are collected in this review. The diverse synthetic approaches are classified according to the size of the ring and taking into account the bond that is formed to complete the quaternary skeleton.
Tetrahedron-asymmetry, 2003
The addition of Et 2 AlCN in the presence of ZnBr 2 or Et 2 AlCl to 1,3-dicarbonyl compounds deri... more The addition of Et 2 AlCN in the presence of ZnBr 2 or Et 2 AlCl to 1,3-dicarbonyl compounds derived from (S)-4-isopropyl-2-oxazolidinone, proceeds with high diastereoselectivity (94-98% de) and good chemical yields. This type of addition to chiral b-dicarbonyl substrates represents a new synthetic methodology leading to the formation of enantiomerically pure cyanohydrins.
Tetrahedron-asymmetry, 2004
An efficient synthesis of both enantiomers of dimethyl d-amino-b-hydroxyethylphosphonate 6 has be... more An efficient synthesis of both enantiomers of dimethyl d-amino-b-hydroxyethylphosphonate 6 has been achieved starting from anthranilic acid, through the resolution of dimethyl (±)-2-(2-N,N-dibenzylaminophenyl)-2-hydroxyethylphosphonate 9 with (S)-O-methylmandelic acid. The absolute configuration of the enantiomers 9 was assigned by the Dale and Mosher approach using the extended Newman projections and molecular mechanics.
![Research paper thumbnail of Diastereoselective reduction of dimethyl γ-[( N- p-toluenesulfonyl)amino]-β-ketophosphonates derived from amino acids](https://attachments.academia-assets.com/47642188/thumbnails/1.jpg)
](Tetrahedron-asymmetry, 2004
Organo-phosphorus compounds S 0080 Diastereoselective Reduction of Dimethyl γ-[(N-p-Toluenesulfon... more Organo-phosphorus compounds S 0080 Diastereoselective Reduction of Dimethyl γ-[(N-p-Toluenesulfonyl)amino]β-ketophosphonates Derived from Amino Acids. -(ORDONEZ*, M.; DE LA CRUZ-CORDERO, R.; FERNANDEZ-ZERTUCHE, M.; MUNOZ-HERNANDEZ, M. A.; GARCIA-BARRADAS, O.; Tetrahedron: Asymmetry 15 (2004) 19, 3035-3043; Cent. Invest. Quim., Univ. Auton. Estado Morelos, 62210 Cuernavaca, Mex.; Eng.) -Klein 11-176
Tetrahedron-asymmetry, 2011
The one-pot three-component reaction of 2-formylbenzoic acid with (S)-and (R)-methylbenzylamine a... more The one-pot three-component reaction of 2-formylbenzoic acid with (S)-and (R)-methylbenzylamine and dimethyl phosphite (Kabachnik-Fields reaction) proceeded in short reaction times under solvent and catalyst free-conditions to afford the corresponding (3R,1 0 S)-and (3S,1 0 R)-isoindolin-1-one-3-phosphonates 3, respectively, in good yield and with high diastereoselectivity (95:5 dr). The use of a solvent decreases the diastereoselectivity and slows the reaction rate. The reaction rate was also influenced by CO 2 H functionality through protonation of the imine intermediate. The absolute configuration at the new stereogenic center was determined by X-ray crystal analysis, and a mechanism was proposed to explain the high diastereoselectivity.
Tetrahedron-asymmetry, 2007
c-Amino acids have attracted considerable attention as biologically active compounds in the centr... more c-Amino acids have attracted considerable attention as biologically active compounds in the central nervous system (CNS) of mammals. Over the last few years, significant interest in the stereoselective synthesis and practical application of linear and cyclic chiral camino acids in the synthesis and design of a,b-and b,c-hybrid peptides with definite secondary structures and design of nanotubes has been reported, thus demonstrating the theoretical interest and the practical importance of c-amino acids. An overview of synthetic approaches to linear and cyclic chiral c-amino acids and derivatives is presented. Data on the practical applications of c-amino acids are also discussed.
Tetrahedron, 2009
An overview of all methodologies published during the last few years focused to the stereoselecti... more An overview of all methodologies published during the last few years focused to the stereoselective (diastereoselective or enantioselective) synthesis of α-aminophosphonic acids and derivatives is reported. The procedures have been classified according a retrosynthetic strategy and taking into account the formation of each one of the bonds connected to the chiral centre.
Tetrahedron-asymmetry, 2007
Chiral phosphonoacetamides bearing (S)-(α-methylbenzyl)benzylamine, (S,S)-bis(α-methylbenzyl )ami... more Chiral phosphonoacetamides bearing (S)-(α-methylbenzyl)benzylamine, (S,S)-bis(α-methylbenzyl )amine, l-phenylglycine methyl ester and l-phenylglycinol were easily prepared in good yield by means of the MichaelisArbuzov reaction of chiral bromoacetamides obtained in ...
Tetrahedron-asymmetry, 2003
An efficient synthesis of both enantiomers of g-amino-b-hydroxypropylphosphonic acid, an analogue... more An efficient synthesis of both enantiomers of g-amino-b-hydroxypropylphosphonic acid, an analogue of GABOB, has been achieved for the first time starting from glycine, through the resolution of dimethyl (±)-3-(N,N-dibenzylamino)-2-hydroxypropylphosphonate 7 with (S)-O-methylmandelic acid.
Tetrahedron-asymmetry, 2004
The reduction of dimethyl 3-N,N-di(a-methylbenzyl)amino-2-ketophosphonates 9 with catecholborane ... more The reduction of dimethyl 3-N,N-di(a-methylbenzyl)amino-2-ketophosphonates 9 with catecholborane at À78°C in presence of LiClO 4 , gave c-amino-b-hydroxyphosphonates 10 and 11 in good yield and with excellent diastereoselectivity. This procedure represents an example of highly diastereoselective 1,4-induction. The hydrolysis and hydrogenation of 10 and 11 afforded the (R)-and (S)-c-amino-b-hydroxypropylphosphonic acid (GABOB P ), respectively.
Tetrahedron-asymmetry, 2010
Tetrahedron-asymmetry, 2008
Reduction of b-keto-diphenylphosphine oxide (S)-4 derived from (S)-mandelic acid with NaBH 4 in m... more Reduction of b-keto-diphenylphosphine oxide (S)-4 derived from (S)-mandelic acid with NaBH 4 in methanol at À78°C gave the anti-3-diphenylphosphinoyl-1,2-diol 6, whereas the reduction of (S)-4 with Zn(BH 4 ) 2 in THF at À78°C afforded the syn-1,2-diol 5, both in high yield and excellent diastereoselectivity. This procedure represents a new approach to the diastereoselective synthesis of diphenylphosphinoyl diols and an example of highly diastereoselective 1,2-induction. A theoretical model to explain the direction and degree of asymmetric induction is proposed.
A new efficient and practical synthesis of syn-and antib,g-dihydroxyphosphonates 1 and 2 was deve... more A new efficient and practical synthesis of syn-and antib,g-dihydroxyphosphonates 1 and 2 was developed in high diastereoselectivity via reduction of b-ketophosphonates readily obtained from (S)-mandelic acid. An example of "diastereoselective 1,2-induction" is showed and a mechanistic model to explain the stereochemical outcome is proposed. Assignment of the configuration at the new stereogenic centers was achieved by 1 H NMR spectral data of their corresponding acetonides.
Tetrahedron-asymmetry, 2003
An efficient synthesis of both enantiomers of g-amino-b-hydroxypropylphosphonic acid, an analogue... more An efficient synthesis of both enantiomers of g-amino-b-hydroxypropylphosphonic acid, an analogue of GABOB, has been achieved for the first time starting from glycine, through the resolution of dimethyl (±)-3-(N,N-dibenzylamino)-2-hydroxypropylphosphonate 7 with (S)-O-methylmandelic acid.
Tetrahedron-asymmetry, 2004
The reduction of dimethyl 3-N,N-di(a-methylbenzyl)amino-2-ketophosphonates 9 with catecholborane ... more The reduction of dimethyl 3-N,N-di(a-methylbenzyl)amino-2-ketophosphonates 9 with catecholborane at À78°C in presence of LiClO 4 , gave c-amino-b-hydroxyphosphonates 10 and 11 in good yield and with excellent diastereoselectivity. This procedure represents an example of highly diastereoselective 1,4-induction. The hydrolysis and hydrogenation of 10 and 11 afforded the (R)-and (S)-c-amino-b-hydroxypropylphosphonic acid (GABOB P ), respectively.
Tetrahedron-asymmetry, 2010
Tetrahedron-asymmetry, 2008
Reduction of b-keto-diphenylphosphine oxide (S)-4 derived from (S)-mandelic acid with NaBH 4 in m... more Reduction of b-keto-diphenylphosphine oxide (S)-4 derived from (S)-mandelic acid with NaBH 4 in methanol at À78°C gave the anti-3-diphenylphosphinoyl-1,2-diol 6, whereas the reduction of (S)-4 with Zn(BH 4 ) 2 in THF at À78°C afforded the syn-1,2-diol 5, both in high yield and excellent diastereoselectivity. This procedure represents a new approach to the diastereoselective synthesis of diphenylphosphinoyl diols and an example of highly diastereoselective 1,2-induction. A theoretical model to explain the direction and degree of asymmetric induction is proposed.
A new efficient and practical synthesis of syn-and antib,g-dihydroxyphosphonates 1 and 2 was deve... more A new efficient and practical synthesis of syn-and antib,g-dihydroxyphosphonates 1 and 2 was developed in high diastereoselectivity via reduction of b-ketophosphonates readily obtained from (S)-mandelic acid. An example of "diastereoselective 1,2-induction" is showed and a mechanistic model to explain the stereochemical outcome is proposed. Assignment of the configuration at the new stereogenic centers was achieved by 1 H NMR spectral data of their corresponding acetonides.
Tetrahedron-asymmetry, 2002
The reduction of g-N,N-dibenzylamino-b-ketophosphonates 4 derived from readily available (S)-trib... more The reduction of g-N,N-dibenzylamino-b-ketophosphonates 4 derived from readily available (S)-tribenzylated amino acids was achieved with catecholborane at -20°C affording g-amino-b-hydroxyphosphonates 5 in high diastereoselectivity and good chemical yield. These reactions provide a new entry to enantiomerically pure g-amino-b-hydroxyphosphonates.
Tetrahedron-asymmetry, 2009
The most recent papers describing the stereoselective synthesis of cyclic quaternary α-amino acid... more The most recent papers describing the stereoselective synthesis of cyclic quaternary α-amino acids are collected in this review. The diverse synthetic approaches are classified according to the size of the ring and taking into account the bond that is formed to complete the quaternary skeleton.
Tetrahedron-asymmetry, 2003
The addition of Et 2 AlCN in the presence of ZnBr 2 or Et 2 AlCl to 1,3-dicarbonyl compounds deri... more The addition of Et 2 AlCN in the presence of ZnBr 2 or Et 2 AlCl to 1,3-dicarbonyl compounds derived from (S)-4-isopropyl-2-oxazolidinone, proceeds with high diastereoselectivity (94-98% de) and good chemical yields. This type of addition to chiral b-dicarbonyl substrates represents a new synthetic methodology leading to the formation of enantiomerically pure cyanohydrins.
Tetrahedron-asymmetry, 2004
An efficient synthesis of both enantiomers of dimethyl d-amino-b-hydroxyethylphosphonate 6 has be... more An efficient synthesis of both enantiomers of dimethyl d-amino-b-hydroxyethylphosphonate 6 has been achieved starting from anthranilic acid, through the resolution of dimethyl (±)-2-(2-N,N-dibenzylaminophenyl)-2-hydroxyethylphosphonate 9 with (S)-O-methylmandelic acid. The absolute configuration of the enantiomers 9 was assigned by the Dale and Mosher approach using the extended Newman projections and molecular mechanics.
Tetrahedron-asymmetry, 2004
Organo-phosphorus compounds S 0080 Diastereoselective Reduction of Dimethyl γ-[(N-p-Toluenesulfon... more Organo-phosphorus compounds S 0080 Diastereoselective Reduction of Dimethyl γ-[(N-p-Toluenesulfonyl)amino]β-ketophosphonates Derived from Amino Acids. -(ORDONEZ*, M.; DE LA CRUZ-CORDERO, R.; FERNANDEZ-ZERTUCHE, M.; MUNOZ-HERNANDEZ, M. A.; GARCIA-BARRADAS, O.; Tetrahedron: Asymmetry 15 (2004) 19, 3035-3043; Cent. Invest. Quim., Univ. Auton. Estado Morelos, 62210 Cuernavaca, Mex.; Eng.) -Klein 11-176
Tetrahedron-asymmetry, 2011
The one-pot three-component reaction of 2-formylbenzoic acid with (S)-and (R)-methylbenzylamine a... more The one-pot three-component reaction of 2-formylbenzoic acid with (S)-and (R)-methylbenzylamine and dimethyl phosphite (Kabachnik-Fields reaction) proceeded in short reaction times under solvent and catalyst free-conditions to afford the corresponding (3R,1 0 S)-and (3S,1 0 R)-isoindolin-1-one-3-phosphonates 3, respectively, in good yield and with high diastereoselectivity (95:5 dr). The use of a solvent decreases the diastereoselectivity and slows the reaction rate. The reaction rate was also influenced by CO 2 H functionality through protonation of the imine intermediate. The absolute configuration at the new stereogenic center was determined by X-ray crystal analysis, and a mechanism was proposed to explain the high diastereoselectivity.
Tetrahedron-asymmetry, 2007
c-Amino acids have attracted considerable attention as biologically active compounds in the centr... more c-Amino acids have attracted considerable attention as biologically active compounds in the central nervous system (CNS) of mammals. Over the last few years, significant interest in the stereoselective synthesis and practical application of linear and cyclic chiral camino acids in the synthesis and design of a,b-and b,c-hybrid peptides with definite secondary structures and design of nanotubes has been reported, thus demonstrating the theoretical interest and the practical importance of c-amino acids. An overview of synthetic approaches to linear and cyclic chiral c-amino acids and derivatives is presented. Data on the practical applications of c-amino acids are also discussed.
Tetrahedron, 2009
An overview of all methodologies published during the last few years focused to the stereoselecti... more An overview of all methodologies published during the last few years focused to the stereoselective (diastereoselective or enantioselective) synthesis of α-aminophosphonic acids and derivatives is reported. The procedures have been classified according a retrosynthetic strategy and taking into account the formation of each one of the bonds connected to the chiral centre.
Tetrahedron-asymmetry, 2007
Chiral phosphonoacetamides bearing (S)-(α-methylbenzyl)benzylamine, (S,S)-bis(α-methylbenzyl )ami... more Chiral phosphonoacetamides bearing (S)-(α-methylbenzyl)benzylamine, (S,S)-bis(α-methylbenzyl )amine, l-phenylglycine methyl ester and l-phenylglycinol were easily prepared in good yield by means of the MichaelisArbuzov reaction of chiral bromoacetamides obtained in ...
Tetrahedron-asymmetry, 2003
An efficient synthesis of both enantiomers of g-amino-b-hydroxypropylphosphonic acid, an analogue... more An efficient synthesis of both enantiomers of g-amino-b-hydroxypropylphosphonic acid, an analogue of GABOB, has been achieved for the first time starting from glycine, through the resolution of dimethyl (±)-3-(N,N-dibenzylamino)-2-hydroxypropylphosphonate 7 with (S)-O-methylmandelic acid.
Tetrahedron-asymmetry, 2004
The reduction of dimethyl 3-N,N-di(a-methylbenzyl)amino-2-ketophosphonates 9 with catecholborane ... more The reduction of dimethyl 3-N,N-di(a-methylbenzyl)amino-2-ketophosphonates 9 with catecholborane at À78°C in presence of LiClO 4 , gave c-amino-b-hydroxyphosphonates 10 and 11 in good yield and with excellent diastereoselectivity. This procedure represents an example of highly diastereoselective 1,4-induction. The hydrolysis and hydrogenation of 10 and 11 afforded the (R)-and (S)-c-amino-b-hydroxypropylphosphonic acid (GABOB P ), respectively.
Tetrahedron-asymmetry, 2010
Tetrahedron-asymmetry, 2008
Reduction of b-keto-diphenylphosphine oxide (S)-4 derived from (S)-mandelic acid with NaBH 4 in m... more Reduction of b-keto-diphenylphosphine oxide (S)-4 derived from (S)-mandelic acid with NaBH 4 in methanol at À78°C gave the anti-3-diphenylphosphinoyl-1,2-diol 6, whereas the reduction of (S)-4 with Zn(BH 4 ) 2 in THF at À78°C afforded the syn-1,2-diol 5, both in high yield and excellent diastereoselectivity. This procedure represents a new approach to the diastereoselective synthesis of diphenylphosphinoyl diols and an example of highly diastereoselective 1,2-induction. A theoretical model to explain the direction and degree of asymmetric induction is proposed.
A new efficient and practical synthesis of syn-and antib,g-dihydroxyphosphonates 1 and 2 was deve... more A new efficient and practical synthesis of syn-and antib,g-dihydroxyphosphonates 1 and 2 was developed in high diastereoselectivity via reduction of b-ketophosphonates readily obtained from (S)-mandelic acid. An example of "diastereoselective 1,2-induction" is showed and a mechanistic model to explain the stereochemical outcome is proposed. Assignment of the configuration at the new stereogenic centers was achieved by 1 H NMR spectral data of their corresponding acetonides.