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Synthesis of N-substituted 3-(2-aryl-2-oxoethyl)-3-hydroxyindolin-2-ones and their conversion to N-substituted (E)-3-(2-aryl-2-oxoethylidene)indolin-2-ones: synthetic sequence, spectroscopic characterization and structures of four 3-hydroxy compounds and five oxoethylidene products

Research output: Contribution to journalArticlepeer-review

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Synthesis of N-substituted 3-(2-aryl-2-oxoethyl)-3-hydroxyindolin-2-ones and their conversion to N-substituted (E)-3-(2-aryl-2-oxoethylidene)indolin-2-ones : synthetic sequence, spectroscopic characterization and structures of four 3-hydroxy compounds and five oxoethylidene products. / Becerra, Diana; Castillo, Juan; Insuasty, Braulio; Cobo, Justo; Glidewell, Christopher.

In: Acta Crystallographica Section C Structural Chemistry, Vol. 76, No. 5, C76, 05.2020.

Research output: Contribution to journalArticlepeer-review

Harvard

Becerra, D, Castillo, J, Insuasty, B, Cobo, J & Glidewell, C 2020, 'Synthesis of N-substituted 3-(2-aryl-2-oxoethyl)-3-hydroxyindolin-2-ones and their conversion to N-substituted (E)-3-(2-aryl-2-oxoethylidene)indolin-2-ones: synthetic sequence, spectroscopic characterization and structures of four 3-hydroxy compounds and five oxoethylidene products', Acta Crystallographica Section C Structural Chemistry, vol. 76, no. 5, C76. https://doi.org/10.1107/S2053229620004143

APA

Becerra, D., Castillo, J., Insuasty, B., Cobo, J., & Glidewell, C. (2020). Synthesis of N-substituted 3-(2-aryl-2-oxoethyl)-3-hydroxyindolin-2-ones and their conversion to N-substituted (E)-3-(2-aryl-2-oxoethylidene)indolin-2-ones: synthetic sequence, spectroscopic characterization and structures of four 3-hydroxy compounds and five oxoethylidene products. Acta Crystallographica Section C Structural Chemistry, 76(5), [C76]. https://doi.org/10.1107/S2053229620004143

Vancouver

Becerra D, Castillo J, Insuasty B, Cobo J, Glidewell C. Synthesis of N-substituted 3-(2-aryl-2-oxoethyl)-3-hydroxyindolin-2-ones and their conversion to N-substituted (E)-3-(2-aryl-2-oxoethylidene)indolin-2-ones: synthetic sequence, spectroscopic characterization and structures of four 3-hydroxy compounds and five oxoethylidene products. Acta Crystallographica Section C Structural Chemistry. 2020 May;76(5). C76. https://doi.org/10.1107/S2053229620004143

Author

Becerra, Diana ; Castillo, Juan ; Insuasty, Braulio ; Cobo, Justo ; Glidewell, Christopher. / Synthesis of N-substituted 3-(2-aryl-2-oxoethyl)-3-hydroxyindolin-2-ones and their conversion to N-substituted (E)-3-(2-aryl-2-oxoethylidene)indolin-2-ones : synthetic sequence, spectroscopic characterization and structures of four 3-hydroxy compounds and five oxoethylidene products. In: Acta Crystallographica Section C Structural Chemistry. 2020 ; Vol. 76, No. 5.

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@article{ae74de09df6640148670752d6156fdd2,
title = "Synthesis of N-substituted 3-(2-aryl-2-oxoethyl)-3-hydroxyindolin-2-ones and their conversion to N-substituted (E)-3-(2-aryl-2-oxoethylidene)indolin-2-ones: synthetic sequence, spectroscopic characterization and structures of four 3-hydroxy compounds and five oxoethylidene products",
abstract = "An operationally simple and time-efficient approach has been developed for the synthesis of racemic N-substituted 3-(2-aryl-2-oxoeth­yl)-3-hy­droxy­indolin-2-ones by a piperidine-catalysed aldol reaction between aryl methyl ketones and N-alkyl­isatins. These aldol products were used successfully as strategic inter­mediates for the preparation of N-substituted (E)-3-(2-hetaryl-2-oxo­ethyl­idene)indolin-2-ones by a stereoselective dehydration reaction under acidic conditions. The products have all been fully characterized by 1H and 13C NMR spectroscopy, by mass spectrometry and, for a representative selection, by crystal structure analysis. In each of (RS)-1-benzyl-3-hy­droxy-3-[2-(4-meth­oxy­phen­yl)-2-oxoeth­yl]indolin-2-one, C24H21NO4, (Ic), and (RS)-1-benzyl-3-{2-[4-(di­methyl­amino)­phen­yl]-2-oxoeth­yl}-3-hy­droxy­indolin-2-one, C25H24N2O3, (Id), inversion-related pairs of mol­ecules are linked by O—H⋯O hydrogen bonds to form R22(10) rings, which are further linked into chains of rings by a combination of C—H⋯O and C—H⋯π(arene) hydrogen bonds in (Ic) and by C—H⋯π(arene) hydrogen bonds in (Id). The mol­ecules of (RS)-1-benzyl-3-hy­droxy-3-[2-oxo-2-(pyridin-4-yl)eth­yl]indolin-2-one, C22H18N2O3, (Ie), are linked into a three-dimensional framework structure by a combination of O—H⋯N, C—H⋯O and C—H⋯π(arene) hydrogen bonds. (RS)-3-[2-(Benzo[d][1,3]dioxol-5-yl)-2-oxoeth­yl]-1-benzyl-3-hy­droxy­indolin-2-one, C24H19NO5, (If), crystallizes with Z′ = 2 in the space group P and the mol­ecules are linked into com­plex sheets by a combination of O—H⋯O, C—H⋯O and C—H⋯π(arene) hydro­gen bonds. In each of (E)-1-benzyl-3-[2-(4-fluoro­phen­yl)-2-oxo­ethyl­idene]indolin-2-one, C23H16FNO2, (IIa), and (E)-1-benzyl-3-[2-oxo-2-(thiophen-2-yl)ethylidene]indolin-2-one, C21H15NO2S, (IIg), the mol­ecules are linked into simple chains by a single C—H⋯O hydrogen bond, while those of (E)-1-benzyl-3-[2-oxo-2-(pyridin-4-yl)ethyl­idene]indolin-2-one, C22H16N2O2, (IIe), are linked by three C—H⋯O hydrogen bonds to form sheets which are further linked into a three-dimensional structure by C—H⋯π(arene) hydrogen bonds. There are no hydrogen bonds in the structures of either (E)-1-benzyl-3-[2-(4-meth­oxy­phen­yl)-2-oxo­ethyl­idene]indolin-2-one, C24H19NO3, (IIc), or (E)-1-benzyl-5-chloro-3-[2-(4-chloro­phen­yl)-2-oxo­ethyl­idene]indolin-2-one, C23H15Cl2NO2, (IIh), but the mol­ecules of (IIh) are linked into chains of π-stacked dimers by a combination of C—Cl⋯π(arene) and aromatic π–π stacking inter­action",
keywords = "Synthesis, Heterocyclic compounds, Isatin, 3-hydroxyindolinone, Molecular structure, Hydrogen bonding, Supramolecular assembly, Crystal structure",
author = "Diana Becerra and Juan Castillo and Braulio Insuasty and Justo Cobo and Christopher Glidewell",
note = "The authors thank `Centro de Instrumentaci{\'o}n Cient{\'i}fico-T{\'e}cnica' of Universidad de Ja{\'e}n and its staff for data collection. They also thank Universidad del Valle, Universidad Pedag{\'o}gica y Tecnol{\'o}gica de Colombia (project SGI-2829), Universidad de Ja{\'e}n and the Consejer{\'i}a de Innovaci{\'o}n, Ciencia y Empresa (Junta de Andaluc{\'i}a, Spain), for financial support. DB also thanks the Asociaci{\'o}n Universitaria Iberoamericana de Postgrado for financial support.",
year = "2020",
month = may,
doi = "10.1107/S2053229620004143",
language = "English",
volume = "76",
journal = "Acta Crystallographica Section C Structural Chemistry",
issn = "2053-2296",
publisher = "International Union of Crystallography",
number = "5",

}

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TY - JOUR

T1 - Synthesis of N-substituted 3-(2-aryl-2-oxoethyl)-3-hydroxyindolin-2-ones and their conversion to N-substituted (E)-3-(2-aryl-2-oxoethylidene)indolin-2-ones

T2 - synthetic sequence, spectroscopic characterization and structures of four 3-hydroxy compounds and five oxoethylidene products

AU - Becerra, Diana

AU - Castillo, Juan

AU - Insuasty, Braulio

AU - Cobo, Justo

AU - Glidewell, Christopher

N1 - The authors thank `Centro de Instrumentación Científico-Técnica' of Universidad de Jaén and its staff for data collection. They also thank Universidad del Valle, Universidad Pedagógica y Tecnológica de Colombia (project SGI-2829), Universidad de Jaén and the Consejería de Innovación, Ciencia y Empresa (Junta de Andalucía, Spain), for financial support. DB also thanks the Asociación Universitaria Iberoamericana de Postgrado for financial support.

PY - 2020/5

Y1 - 2020/5

N2 - An operationally simple and time-efficient approach has been developed for the synthesis of racemic N-substituted 3-(2-aryl-2-oxoeth­yl)-3-hy­droxy­indolin-2-ones by a piperidine-catalysed aldol reaction between aryl methyl ketones and N-alkyl­isatins. These aldol products were used successfully as strategic inter­mediates for the preparation of N-substituted (E)-3-(2-hetaryl-2-oxo­ethyl­idene)indolin-2-ones by a stereoselective dehydration reaction under acidic conditions. The products have all been fully characterized by 1H and 13C NMR spectroscopy, by mass spectrometry and, for a representative selection, by crystal structure analysis. In each of (RS)-1-benzyl-3-hy­droxy-3-[2-(4-meth­oxy­phen­yl)-2-oxoeth­yl]indolin-2-one, C24H21NO4, (Ic), and (RS)-1-benzyl-3-{2-[4-(di­methyl­amino)­phen­yl]-2-oxoeth­yl}-3-hy­droxy­indolin-2-one, C25H24N2O3, (Id), inversion-related pairs of mol­ecules are linked by O—H⋯O hydrogen bonds to form R22(10) rings, which are further linked into chains of rings by a combination of C—H⋯O and C—H⋯π(arene) hydrogen bonds in (Ic) and by C—H⋯π(arene) hydrogen bonds in (Id). The mol­ecules of (RS)-1-benzyl-3-hy­droxy-3-[2-oxo-2-(pyridin-4-yl)eth­yl]indolin-2-one, C22H18N2O3, (Ie), are linked into a three-dimensional framework structure by a combination of O—H⋯N, C—H⋯O and C—H⋯π(arene) hydrogen bonds. (RS)-3-[2-(Benzo[d][1,3]dioxol-5-yl)-2-oxoeth­yl]-1-benzyl-3-hy­droxy­indolin-2-one, C24H19NO5, (If), crystallizes with Z′ = 2 in the space group P and the mol­ecules are linked into com­plex sheets by a combination of O—H⋯O, C—H⋯O and C—H⋯π(arene) hydro­gen bonds. In each of (E)-1-benzyl-3-[2-(4-fluoro­phen­yl)-2-oxo­ethyl­idene]indolin-2-one, C23H16FNO2, (IIa), and (E)-1-benzyl-3-[2-oxo-2-(thiophen-2-yl)ethylidene]indolin-2-one, C21H15NO2S, (IIg), the mol­ecules are linked into simple chains by a single C—H⋯O hydrogen bond, while those of (E)-1-benzyl-3-[2-oxo-2-(pyridin-4-yl)ethyl­idene]indolin-2-one, C22H16N2O2, (IIe), are linked by three C—H⋯O hydrogen bonds to form sheets which are further linked into a three-dimensional structure by C—H⋯π(arene) hydrogen bonds. There are no hydrogen bonds in the structures of either (E)-1-benzyl-3-[2-(4-meth­oxy­phen­yl)-2-oxo­ethyl­idene]indolin-2-one, C24H19NO3, (IIc), or (E)-1-benzyl-5-chloro-3-[2-(4-chloro­phen­yl)-2-oxo­ethyl­idene]indolin-2-one, C23H15Cl2NO2, (IIh), but the mol­ecules of (IIh) are linked into chains of π-stacked dimers by a combination of C—Cl⋯π(arene) and aromatic π–π stacking inter­action

AB - An operationally simple and time-efficient approach has been developed for the synthesis of racemic N-substituted 3-(2-aryl-2-oxoeth­yl)-3-hy­droxy­indolin-2-ones by a piperidine-catalysed aldol reaction between aryl methyl ketones and N-alkyl­isatins. These aldol products were used successfully as strategic inter­mediates for the preparation of N-substituted (E)-3-(2-hetaryl-2-oxo­ethyl­idene)indolin-2-ones by a stereoselective dehydration reaction under acidic conditions. The products have all been fully characterized by 1H and 13C NMR spectroscopy, by mass spectrometry and, for a representative selection, by crystal structure analysis. In each of (RS)-1-benzyl-3-hy­droxy-3-[2-(4-meth­oxy­phen­yl)-2-oxoeth­yl]indolin-2-one, C24H21NO4, (Ic), and (RS)-1-benzyl-3-{2-[4-(di­methyl­amino)­phen­yl]-2-oxoeth­yl}-3-hy­droxy­indolin-2-one, C25H24N2O3, (Id), inversion-related pairs of mol­ecules are linked by O—H⋯O hydrogen bonds to form R22(10) rings, which are further linked into chains of rings by a combination of C—H⋯O and C—H⋯π(arene) hydrogen bonds in (Ic) and by C—H⋯π(arene) hydrogen bonds in (Id). The mol­ecules of (RS)-1-benzyl-3-hy­droxy-3-[2-oxo-2-(pyridin-4-yl)eth­yl]indolin-2-one, C22H18N2O3, (Ie), are linked into a three-dimensional framework structure by a combination of O—H⋯N, C—H⋯O and C—H⋯π(arene) hydrogen bonds. (RS)-3-[2-(Benzo[d][1,3]dioxol-5-yl)-2-oxoeth­yl]-1-benzyl-3-hy­droxy­indolin-2-one, C24H19NO5, (If), crystallizes with Z′ = 2 in the space group P and the mol­ecules are linked into com­plex sheets by a combination of O—H⋯O, C—H⋯O and C—H⋯π(arene) hydro­gen bonds. In each of (E)-1-benzyl-3-[2-(4-fluoro­phen­yl)-2-oxo­ethyl­idene]indolin-2-one, C23H16FNO2, (IIa), and (E)-1-benzyl-3-[2-oxo-2-(thiophen-2-yl)ethylidene]indolin-2-one, C21H15NO2S, (IIg), the mol­ecules are linked into simple chains by a single C—H⋯O hydrogen bond, while those of (E)-1-benzyl-3-[2-oxo-2-(pyridin-4-yl)ethyl­idene]indolin-2-one, C22H16N2O2, (IIe), are linked by three C—H⋯O hydrogen bonds to form sheets which are further linked into a three-dimensional structure by C—H⋯π(arene) hydrogen bonds. There are no hydrogen bonds in the structures of either (E)-1-benzyl-3-[2-(4-meth­oxy­phen­yl)-2-oxo­ethyl­idene]indolin-2-one, C24H19NO3, (IIc), or (E)-1-benzyl-5-chloro-3-[2-(4-chloro­phen­yl)-2-oxo­ethyl­idene]indolin-2-one, C23H15Cl2NO2, (IIh), but the mol­ecules of (IIh) are linked into chains of π-stacked dimers by a combination of C—Cl⋯π(arene) and aromatic π–π stacking inter­action

KW - Synthesis

KW - Heterocyclic compounds

KW - Isatin

KW - 3-hydroxyindolinone

KW - Molecular structure

KW - Hydrogen bonding

KW - Supramolecular assembly

KW - Crystal structure

U2 - 10.1107/S2053229620004143

DO - 10.1107/S2053229620004143

M3 - Article

VL - 76

JO - Acta Crystallographica Section C Structural Chemistry

JF - Acta Crystallographica Section C Structural Chemistry

SN - 2053-2296

IS - 5

M1 - C76

ER -

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