title: Frozen Chirality of Tertiary Aromatic Amides: Access to Enantioenriched Tertiary α-Amino Acid or Amino Alcohol without Chiral Reagent.
abstract: One of the fundamental and intriguing aspects of life is the homochirality of the essential molecules. In this field, the absolute asymmetric synthesis of α-amino acids is a major challenge. Herein, we report access, by chemical means, to tertiary α-amino acid derivatives in up to 96 % ee without using any chiral reagent. In our strategy, the dynamic axial chirality of tertiary aromatic amides is frozen in a crystal and is responsible for the stereoselectivity of the subsequent steps. Furthermore, we could control the configuration of the final product by manually sorting and selecting the initial crystals. Based on vibrational circular dichroism studies, we could rationalize the observed stereoselectivity.
authors.affiliation: Univ. Paris-Sud, Laboratoire de Méthodologie, Synthèse et Molécules Thérapeutiques, ICMMO, UMR 8182, CNRS, Université Paris-Saclay, Bât 410, 91405, Orsay, France.
authors.forename: Thi Thoa
authors.initials: TT
authors.lastname: Mai
authors.affiliation: Univ. Paris-Sud, Laboratoire de Méthodologie, Synthèse et Molécules Thérapeutiques, ICMMO, UMR 8182, CNRS, Université Paris-Saclay, Bât 410, 91405, Orsay, France.
authors.forename: Baby
authors.initials: B
authors.lastname: Viswambharan
authors.affiliation: Univ. Paris-Sud, Laboratoire de Méthodologie, Synthèse et Molécules Thérapeutiques, ICMMO, UMR 8182, CNRS, Université Paris-Saclay, Bât 410, 91405, Orsay, France.
authors.forename: Didier
authors.initials: D
authors.lastname: Gori
authors.affiliation: Univ. Paris-Sud, Laboratoire de Méthodologie, Synthèse et Molécules Thérapeutiques, ICMMO, UMR 8182, CNRS, Université Paris-Saclay, Bât 410, 91405, Orsay, France.
authors.forename: Régis
authors.initials: R
authors.lastname: Guillot
authors.affiliation: Aix Marseille Université, Centrale Marseille, CNRS-Spectropole, FR1739, 13397, Marseille, France.
authors.forename: Jean-Valère
authors.initials: JV
authors.lastname: Naubron
authors.affiliation: Univ. Paris-Sud, Laboratoire de Méthodologie, Synthèse et Molécules Thérapeutiques, ICMMO, UMR 8182, CNRS, Université Paris-Saclay, Bât 410, 91405, Orsay, France.
authors.forename: Cyrille
authors.initials: C
authors.lastname: Kouklovsky
authors.affiliation: Univ. Paris-Sud, Laboratoire de Méthodologie, Synthèse et Molécules Thérapeutiques, ICMMO, UMR 8182, CNRS, Université Paris-Saclay, Bât 410, 91405, Orsay, France.
authors.forename: Valérie
authors.initials: V
authors.lastname: Alezra
mesh_terms: D000577:Amides / Q000138:chemical synthesis / Q000737:chemistry*; D000596:Amino Acids / Q000737:chemistry*; D000605:Amino Alcohols / Q000737:chemistry*; D002942:Circular Dichroism; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D023303:Oxazolidinones / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000577:Amides; D000596:Amino Acids; D000605:Amino Alcohols; D023303:Oxazolidinones
keywords: amino acids; amino alcohols; asymmetric amplification; asymmetric synthesis; chirality