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Direct asymmetric intermolecular aldol reactions catalyzed by amino acids and small peptides.
Chemistry. 2006 Jul 05; 12(20):5383-97.C

Abstract

In nature there are at least nineteen different acyclic amino acids that act as the building blocks of polypeptides and proteins with different functions. Here we report that alpha-amino acids, beta-amino acids, and chiral amines containing primary amine functions catalyze direct asymmetric intermolecular aldol reactions with high enantioselectivities. Moreover, the amino acids can be combined into highly modular natural and unusual small peptides that also catalyze direct asymmetric intermolecular aldol reactions with high stereoselectivities, to furnish the corresponding aldol products with up to >99 % ee. Simple amino acids and small peptides can thus catalyze asymmetric aldol reactions with stereoselectivities matching those of natural enzymes that have evolved over billions of years. A small amount of water accelerates the asymmetric aldol reactions catalyzed by amino acids and small peptides, and also increases their stereoselectivities. Notably, small peptides and amino acid tetrazoles were able to catalyze direct asymmetric aldol reactions with high enantioselectivities in water, while the parent amino acids, in stark contrast, furnished nearly racemic products. These results suggest that the prebiotic oligomerization of amino acids to peptides may plausibly have been a link in the evolution of the homochirality of sugars. The mechanism and stereochemistry of the reactions are also discussed.

Authors+Show Affiliations

Department of Organic Chemistry, The Arrhenius Laboratory, Stockholm University, 106 91 Stockholm, Sweden. acordova@organ.su.seNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

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

Language

eng

PubMed ID

16637082

Citation

Córdova, Armando, et al. "Direct Asymmetric Intermolecular Aldol Reactions Catalyzed By Amino Acids and Small Peptides." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 12, no. 20, 2006, pp. 5383-97.
Córdova A, Zou W, Dziedzic P, et al. Direct asymmetric intermolecular aldol reactions catalyzed by amino acids and small peptides. Chemistry. 2006;12(20):5383-97.
Córdova, A., Zou, W., Dziedzic, P., Ibrahem, I., Reyes, E., & Xu, Y. (2006). Direct asymmetric intermolecular aldol reactions catalyzed by amino acids and small peptides. Chemistry (Weinheim an Der Bergstrasse, Germany), 12(20), 5383-97.
Córdova A, et al. Direct Asymmetric Intermolecular Aldol Reactions Catalyzed By Amino Acids and Small Peptides. Chemistry. 2006 Jul 5;12(20):5383-97. PubMed PMID: 16637082.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Direct asymmetric intermolecular aldol reactions catalyzed by amino acids and small peptides. AU - Córdova,Armando, AU - Zou,Weibiao, AU - Dziedzic,Pawel, AU - Ibrahem,Ismail, AU - Reyes,Efraim, AU - Xu,Yongmei, PY - 2006/4/26/pubmed PY - 2007/6/7/medline PY - 2006/4/26/entrez SP - 5383 EP - 97 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 12 IS - 20 N2 - In nature there are at least nineteen different acyclic amino acids that act as the building blocks of polypeptides and proteins with different functions. Here we report that alpha-amino acids, beta-amino acids, and chiral amines containing primary amine functions catalyze direct asymmetric intermolecular aldol reactions with high enantioselectivities. Moreover, the amino acids can be combined into highly modular natural and unusual small peptides that also catalyze direct asymmetric intermolecular aldol reactions with high stereoselectivities, to furnish the corresponding aldol products with up to >99 % ee. Simple amino acids and small peptides can thus catalyze asymmetric aldol reactions with stereoselectivities matching those of natural enzymes that have evolved over billions of years. A small amount of water accelerates the asymmetric aldol reactions catalyzed by amino acids and small peptides, and also increases their stereoselectivities. Notably, small peptides and amino acid tetrazoles were able to catalyze direct asymmetric aldol reactions with high enantioselectivities in water, while the parent amino acids, in stark contrast, furnished nearly racemic products. These results suggest that the prebiotic oligomerization of amino acids to peptides may plausibly have been a link in the evolution of the homochirality of sugars. The mechanism and stereochemistry of the reactions are also discussed. SN - 0947-6539 UR - https://www.unboundmedicine.com/medline/citation/16637082/Direct_asymmetric_intermolecular_aldol_reactions_catalyzed_by_amino_acids_and_small_peptides_ L2 - https://doi.org/10.1002/chem.200501639 DB - PRIME DP - Unbound Medicine ER -