Abstract:
The first catalytic enantioselective pinacol rearrangement was reported by Antilla and co-workers in 2010. The reaction was catalyzed by a chiral phosphoric acid and resulted in high levels of enantioselectivity (up to 96% ee). The present study uses density functional theory to investigate the mechanism and origins of stereoselectivity of this important reaction and to explain the difference in selectivity between different catalysts. An OH···O hydrogen bond between the intermediate indolyl alcohol and the phosphate group from the catalyst together with a CH···O hydrogen bond between the indole and the phosphate group were observed in the preferred activation mode for the stereodetermining [1,2]-aryl shift. A stronger CH···O interaction in the major transition state was found to contribute to the high levels of enantioselectivity. A more bulky catalyst (TRIP) was found to impede the formation of the key CH···O interaction, leading to lower levels of enantioselectivity. © 2018 American Chemical Society.
Registro:
Documento: |
Artículo
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Título: | Mechanistic Insights into a Chiral Phosphoric Acid-Catalyzed Asymmetric Pinacol Rearrangement |
Autor: | Falcone, B.N.; Grayson, M.N.; Rodriguez, J.B. |
Filiación: | Departamento de Química Orgánica and UMYMFOR (CONICET-FCEyN), Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, Buenos Aires, C1428EHA, Argentina Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, United Kingdom
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Palabras clave: | Catalysis; Catalyst selectivity; Cyclization; Density functional theory; Hydrogen bonds; Phosphoric acid; Enantioselective; Phosphate group; Pinacol rearrangements; Transition state; Enantioselectivity; alcohol; indole; phosphate; phosphoric acid; Article; asymmetric catalysis; chirality; conformation; density functional theory; enantioselectivity; hydrogen bond; molecular dynamics; pinacol rearrangement; reaction analysis; stereoselectivity |
Año: | 2018
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Volumen: | 83
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Número: | 23
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Página de inicio: | 14683
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Página de fin: | 14687
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DOI: |
http://dx.doi.org/10.1021/acs.joc.8b02812 |
Título revista: | Journal of Organic Chemistry
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Título revista abreviado: | J. Org. Chem.
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ISSN: | 00223263
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CODEN: | JOCEA
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CAS: | alcohol, 64-17-5; indole, 120-72-9; phosphate, 14066-19-4, 14265-44-2; phosphoric acid, 7664-38-2
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Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v83_n23_p14683_Falcone |
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Citas:
---------- APA ----------
Falcone, B.N., Grayson, M.N. & Rodriguez, J.B.
(2018)
. Mechanistic Insights into a Chiral Phosphoric Acid-Catalyzed Asymmetric Pinacol Rearrangement. Journal of Organic Chemistry, 83(23), 14683-14687.
http://dx.doi.org/10.1021/acs.joc.8b02812---------- CHICAGO ----------
Falcone, B.N., Grayson, M.N., Rodriguez, J.B.
"Mechanistic Insights into a Chiral Phosphoric Acid-Catalyzed Asymmetric Pinacol Rearrangement"
. Journal of Organic Chemistry 83, no. 23
(2018) : 14683-14687.
http://dx.doi.org/10.1021/acs.joc.8b02812---------- MLA ----------
Falcone, B.N., Grayson, M.N., Rodriguez, J.B.
"Mechanistic Insights into a Chiral Phosphoric Acid-Catalyzed Asymmetric Pinacol Rearrangement"
. Journal of Organic Chemistry, vol. 83, no. 23, 2018, pp. 14683-14687.
http://dx.doi.org/10.1021/acs.joc.8b02812---------- VANCOUVER ----------
Falcone, B.N., Grayson, M.N., Rodriguez, J.B. Mechanistic Insights into a Chiral Phosphoric Acid-Catalyzed Asymmetric Pinacol Rearrangement. J. Org. Chem. 2018;83(23):14683-14687.
http://dx.doi.org/10.1021/acs.joc.8b02812