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Amino acid catalyzed neogenesis of carbohydrates: a plausible ancient transformation.
Chemistry. 2005 Aug 05; 11(16):4772-84.C

Abstract

Hexose sugars play a fundamental role in vital biochemical processes and their biosynthesis is achieved through enzyme-catalyzed pathways. Herein we disclose the ability of amino acids to catalyze the asymmetric neogenesis of carbohydrates by sequential cross-aldol reactions. The amino acids mediate the asymmetric de novo synthesis of natural L- and D-hexoses and their analogues with excellent stereoselectivity in organic solvents. In some cases, the four new stereocenters are assembled with almost absolute stereocontrol. The unique feature of these results is that, when an amino acid is employed as the catalyst, a single reaction sequence can convert a protected glycol aldehyde into a hexose in one step. For example, proline and its derivatives catalyze the asymmetric neogenesis of allose with >99 % ee in one chemical manipulation. Furthermore, all amino acids tested catalyzed the asymmetric formation of natural sugars under prebiotic conditions, with alanine being the smallest catalyst. The inherent simplicity of this catalytic process suggests that a catalytic prebiotic "gluconeogenesis" may occur, in which amino acids transfer their stereochemical information to sugars. In addition, the amino acid catalyzed stereoselective sequential cross-aldol reactions were performed as a two-step procedure with different aldehydes as acceptors and nucleophiles. The employment of two different amino acids as catalysts for the iterative direct aldol reactions enabled the asymmetric synthesis of deoxysugars with >99 % ee. In addition, the direct amino acid catalyzed C(2)+C(2)+C(2) methodology is a new entry for the short, highly enantioselective de novo synthesis of carbohydrate derivatives, isotope-labeled sugars, and polyketide natural products. The one-pot asymmetric de novo syntheses of deoxy and polyketide carbohydrates involved a novel dynamic kinetic asymmetric transformation (DYKAT) mediated by an amino acid.

Authors+Show Affiliations

Córdova A
Department of Organic Chemistry, The Arrhenius Laboratory, Stockholm University, Sweden. accordova@organ.su.se
Ibrahem I
No affiliation info available
Casas J
No affiliation info available
Sundén H
No affiliation info available
Engqvist M
No affiliation info available
Reyes E
No affiliation info available

MeSH

Amino AcidsEvolution, MolecularMolecular ConformationOligosaccharidesSolventsWater

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

15929141

Citation

Córdova, Armando, et al. "Amino Acid Catalyzed Neogenesis of Carbohydrates: a Plausible Ancient Transformation." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 11, no. 16, 2005, pp. 4772-84.
Córdova A, Ibrahem I, Casas J, et al. Amino acid catalyzed neogenesis of carbohydrates: a plausible ancient transformation. Chemistry. 2005;11(16):4772-84.
Córdova, A., Ibrahem, I., Casas, J., Sundén, H., Engqvist, M., & Reyes, E. (2005). Amino acid catalyzed neogenesis of carbohydrates: a plausible ancient transformation. Chemistry (Weinheim an Der Bergstrasse, Germany), 11(16), 4772-84.
Córdova A, et al. Amino Acid Catalyzed Neogenesis of Carbohydrates: a Plausible Ancient Transformation. Chemistry. 2005 Aug 5;11(16):4772-84. PubMed PMID: 15929141.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Amino acid catalyzed neogenesis of carbohydrates: a plausible ancient transformation. AU - Córdova,Armando, AU - Ibrahem,Ismail, AU - Casas,Jesús, AU - Sundén,Henrik, AU - Engqvist,Magnus, AU - Reyes,Efraim, PY - 2005/6/2/pubmed PY - 2007/1/11/medline PY - 2005/6/2/entrez SP - 4772 EP - 84 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 11 IS - 16 N2 - Hexose sugars play a fundamental role in vital biochemical processes and their biosynthesis is achieved through enzyme-catalyzed pathways. Herein we disclose the ability of amino acids to catalyze the asymmetric neogenesis of carbohydrates by sequential cross-aldol reactions. The amino acids mediate the asymmetric de novo synthesis of natural L- and D-hexoses and their analogues with excellent stereoselectivity in organic solvents. In some cases, the four new stereocenters are assembled with almost absolute stereocontrol. The unique feature of these results is that, when an amino acid is employed as the catalyst, a single reaction sequence can convert a protected glycol aldehyde into a hexose in one step. For example, proline and its derivatives catalyze the asymmetric neogenesis of allose with >99 % ee in one chemical manipulation. Furthermore, all amino acids tested catalyzed the asymmetric formation of natural sugars under prebiotic conditions, with alanine being the smallest catalyst. The inherent simplicity of this catalytic process suggests that a catalytic prebiotic "gluconeogenesis" may occur, in which amino acids transfer their stereochemical information to sugars. In addition, the amino acid catalyzed stereoselective sequential cross-aldol reactions were performed as a two-step procedure with different aldehydes as acceptors and nucleophiles. The employment of two different amino acids as catalysts for the iterative direct aldol reactions enabled the asymmetric synthesis of deoxysugars with >99 % ee. In addition, the direct amino acid catalyzed C(2)+C(2)+C(2) methodology is a new entry for the short, highly enantioselective de novo synthesis of carbohydrate derivatives, isotope-labeled sugars, and polyketide natural products. The one-pot asymmetric de novo syntheses of deoxy and polyketide carbohydrates involved a novel dynamic kinetic asymmetric transformation (DYKAT) mediated by an amino acid. SN - 0947-6539 UR - https://www.unboundmedicine.com/medline/citation/15929141/Amino_acid_catalyzed_neogenesis_of_carbohydrates:_a_plausible_ancient_transformation_ DB - PRIME DP - Unbound Medicine ER -