Schiff Bases and Stereocontrolled Formation of Fused 1,3-Oxazolidines from 1-Amino-2-Indanol: A Systematic Study on Structure and Mechanism
Schiff Bases and Stereocontrolled Formation of Fused 1,3-Oxazolidines from 1-Amino-2-Indanol: A Systematic Study on Structure and Mechanism
This paper thoroughly explores the formation of Schiff bases derived from salicylaldehydes and a conformationally restricted amino alcohol (1-amino-2-indanol), as well as the generation of 1,3-oxazolidines, a key heterocyclic core present in numerous bioactive compounds. We provide enough evidences, both experimental-including crystallographic analyses and DFT-based calculations on imine/enamine tautomerism in the solid state and solution. In the course of imine formation, a pentacyclic oxazolidine–oxazine structure could be isolated with complete stereocontrol, whose configuration has been determined by merging theory and experiment. Mechanistic studies reveal that, although oxazolidines can be obtained under kinetic conditions, the prevalence of imines obeys to thermodynamic control as they are the most stable structures. The stereochemical outcome of imine cyclization under acylating conditions leads to formation of 2,4-trans-oxazolidines.
aminoindanols, DFT calculations, oxazolidines, Schiff bases, stereochemistry, tautomeric equilibria
Matamoros, Esther
67ecaf15-3e62-46d8-b8fd-717f8e8c439a
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Cintas, Pedro
8b9e8dcb-111f-4baa-8736-502d4b75b563
Palacios, Juan C.
2c06e379-89b3-46b1-95c8-7f5057732f9f
9 February 2023
Matamoros, Esther
67ecaf15-3e62-46d8-b8fd-717f8e8c439a
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Cintas, Pedro
8b9e8dcb-111f-4baa-8736-502d4b75b563
Palacios, Juan C.
2c06e379-89b3-46b1-95c8-7f5057732f9f
Matamoros, Esther, Light, Mark E., Cintas, Pedro and Palacios, Juan C.
(2023)
Schiff Bases and Stereocontrolled Formation of Fused 1,3-Oxazolidines from 1-Amino-2-Indanol: A Systematic Study on Structure and Mechanism.
Molecules, 28 (4), [1670].
(doi:10.3390/molecules28041670).
Abstract
This paper thoroughly explores the formation of Schiff bases derived from salicylaldehydes and a conformationally restricted amino alcohol (1-amino-2-indanol), as well as the generation of 1,3-oxazolidines, a key heterocyclic core present in numerous bioactive compounds. We provide enough evidences, both experimental-including crystallographic analyses and DFT-based calculations on imine/enamine tautomerism in the solid state and solution. In the course of imine formation, a pentacyclic oxazolidine–oxazine structure could be isolated with complete stereocontrol, whose configuration has been determined by merging theory and experiment. Mechanistic studies reveal that, although oxazolidines can be obtained under kinetic conditions, the prevalence of imines obeys to thermodynamic control as they are the most stable structures. The stereochemical outcome of imine cyclization under acylating conditions leads to formation of 2,4-trans-oxazolidines.
Text
molecules-28-01670-v2
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Accepted/In Press date: 31 January 2023
Published date: 9 February 2023
Additional Information:
Funding Information:
This research was funded by the Junta de Extremadura and Fondo Europeo de Desarrollo Regional (Grant GR21039).
Funding Information:
We gratefully acknowledge the Servicio de Apoyo a la Investigación (SAIUEX) at the University of Extremadura for analytical and spectroscopic resources, and the computational facilities at the LUSITANIA Supercomputing Centre supported by Cenits and Computaex Foundation. Last, but not least, this manuscript is dedicated to the memory of María Dolores Méndez.
Publisher Copyright:
© 2023 by the authors.
Keywords:
aminoindanols, DFT calculations, oxazolidines, Schiff bases, stereochemistry, tautomeric equilibria
Identifiers
Local EPrints ID: 476172
URI: http://eprints.soton.ac.uk/id/eprint/476172
ISSN: 1420-3049
PURE UUID: 078dacdf-1406-45e5-bfc9-1d18b36d6334
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Date deposited: 13 Apr 2023 16:33
Last modified: 18 Mar 2024 02:50
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Contributors
Author:
Esther Matamoros
Author:
Pedro Cintas
Author:
Juan C. Palacios
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