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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
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
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
Volumen:83
Número:23
Página de inicio:14683
Página de fin:14687
DOI: http://dx.doi.org/10.1021/acs.joc.8b02812
Título revista:Journal of Organic Chemistry
Título revista abreviado:J. Org. Chem.
ISSN:00223263
CODEN:JOCEA
CAS:alcohol, 64-17-5; indole, 120-72-9; phosphate, 14066-19-4, 14265-44-2; phosphoric acid, 7664-38-2
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