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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
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...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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International Union of Crystallography
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7199199/ https://www.ncbi.nlm.nih.gov/pubmed/32367824 http://dx.doi.org/10.1107/S2053229620004143 |
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author | Becerra, Diana Castillo, Juan Insuasty, Braulio Cobo, Justo Glidewell, Christopher |
author_facet | Becerra, Diana Castillo, Juan Insuasty, Braulio Cobo, Justo Glidewell, Christopher |
author_sort | Becerra, Diana |
collection | PubMed |
description | 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 (1)H and (13)C 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, C(24)H(21)NO(4), (Ic), and (RS)-1-benzyl-3-{2-[4-(dimethylamino)phenyl]-2-oxoethyl}-3-hydroxyindolin-2-one, C(25)H(24)N(2)O(3), (Id), inversion-related pairs of molecules are linked by O—H⋯O hydrogen bonds to form R (2) (2)(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, C(22)H(18)N(2)O(3), (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, C(24)H(19)NO(5), (If), crystallizes with Z′ = 2 in the space group P [Image: see text] 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, C(23)H(16)FNO(2), (IIa), and (E)-1-benzyl-3-[2-oxo-2-(thiophen-2-yl)ethylidene]indolin-2-one, C(21)H(15)NO(2)S, (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, C(22)H(16)N(2)O(2), (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, C(24)H(19)NO(3), (IIc), or (E)-1-benzyl-5-chloro-3-[2-(4-chlorophenyl)-2-oxoethylidene]indolin-2-one, C(23)H(15)Cl(2)NO(2), (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 interactions. |
format | Online Article Text |
id | pubmed-7199199 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | International Union of Crystallography |
record_format | MEDLINE/PubMed |
spelling | pubmed-71991992020-05-19 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 Acta Crystallogr C Struct Chem Research Papers 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 (1)H and (13)C 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, C(24)H(21)NO(4), (Ic), and (RS)-1-benzyl-3-{2-[4-(dimethylamino)phenyl]-2-oxoethyl}-3-hydroxyindolin-2-one, C(25)H(24)N(2)O(3), (Id), inversion-related pairs of molecules are linked by O—H⋯O hydrogen bonds to form R (2) (2)(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, C(22)H(18)N(2)O(3), (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, C(24)H(19)NO(5), (If), crystallizes with Z′ = 2 in the space group P [Image: see text] 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, C(23)H(16)FNO(2), (IIa), and (E)-1-benzyl-3-[2-oxo-2-(thiophen-2-yl)ethylidene]indolin-2-one, C(21)H(15)NO(2)S, (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, C(22)H(16)N(2)O(2), (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, C(24)H(19)NO(3), (IIc), or (E)-1-benzyl-5-chloro-3-[2-(4-chlorophenyl)-2-oxoethylidene]indolin-2-one, C(23)H(15)Cl(2)NO(2), (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 interactions. International Union of Crystallography 2020-04-20 /pmc/articles/PMC7199199/ /pubmed/32367824 http://dx.doi.org/10.1107/S2053229620004143 Text en © Becerra et al. 2020 http://creativecommons.org/licenses/by/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.http://creativecommons.org/licenses/by/4.0/ |
spellingShingle | Research Papers 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 |
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 |
title_full | 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 |
title_fullStr | 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 |
title_full_unstemmed | 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 |
title_short | 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 |
title_sort | 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 |
topic | Research Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7199199/ https://www.ncbi.nlm.nih.gov/pubmed/32367824 http://dx.doi.org/10.1107/S2053229620004143 |
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