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dc.contributor.author
Karak, Milandip
dc.contributor.author
Acosta, Jaime A. M.
dc.contributor.author
Barbosa, Luiz C. A.
dc.contributor.author
Sarotti, Ariel Marcelo
dc.contributor.author
Da Silva, Cameron C.
dc.contributor.author
Boukouvalas, John
dc.contributor.author
Martins, Felipe T.
dc.date.available
2018-07-20T15:07:06Z
dc.date.issued
2016-10
dc.identifier.citation
Karak, Milandip; Acosta, Jaime A. M.; Barbosa, Luiz C. A.; Sarotti, Ariel Marcelo; Da Silva, Cameron C.; et al.; Substituent-Modulated Conformation and Supramolecular Assembly of Tetronamides; American Chemical Society; Crystal Growth & Design; 16; 10; 10-2016; 5798-5810
dc.identifier.issn
1528-7483
dc.identifier.uri
http://hdl.handle.net/11336/52726
dc.description.abstract
The crystal structures of nine compounds (1-9) bearing the 4-aminofuran-2(5H)-one scaffold (commonly known as tetronamide, C4H5NO2) and two decorating aromatic/heteroaromatic moieties with two stereocenters have been determined. Tetronamides bearing at the 5-position a phenyl moiety (1 and 2, 3-chloro derivatives with either a 4-p-tolylamino or 4-p-bromophenylamino substituent), an o-bromopyridyl moiety (3, a 3-bromo-4-p-tolylamino derivative), or an o-tolyl moiety (4, a 3-bromo-4-p-tolylamino derivative) adopt a U-shaped conformation. This conformation is stabilized by an intramolecular contact involving either the phenyl o-CH moiety (1 and 2) or the substituent at the ortho position (3 and 4) and the π system of the N-phenyl ring. The other five tetronamides (5-9) are not present with such an intramolecular contact. In fact, these last five compounds are not U-shaped and feature the presence at the 5-position of a p-biphenyl moiety (5 and 7, 3-bromo-4-p-tolylamino diastereomers differing as 5R and 5S), a p-methoxyphenyl moiety (6, a 3-chloro-4-p-bromophenylamino derivative), or a 5-chlorofuran-2-yl moiety (8 and 9, 3-chloro-4-p-tolylamino diastereomers differing as 5R and 5S). Crystal structures of a 5,5-disubstituted tetronamide bearing m-nitrophenyl moieties (10) and a parent tetronamide without a substituent at the 5-position (11d) reinforce the conformational trend found in 1-9. Furthermore, OH···O centrosymmetric dimers are formed only in the crystal structures of the U-shaped tetronamides. Chain motifs assembled through OH···O and NH···O hydrogen bonds are preferred in the line-shaped tetronamides. Furthermore, the conformer energies were calculated in both the gas and solution phases (B3LYP/6-31G∗). The lowest-energy conformations feature an intramolecular N-H···O hydrogen bond as in the crystal structure of 7. In the U-shaped tetronamides, the crystal structure conformations are similar to the third or fourth energetically ranked stable calculated conformer. Therefore, it is concluded that the substitution pattern in the U-shaped tetronamides allows for accessible secondary minimum-energy conformations that are easily adopted in the crystal structure as a result of their compatibility with the robust centrosymmetric O-H···O dimer formation.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Tetronamides
dc.subject
Supramolecular Assembly
dc.subject
X-Ray Crystallography
dc.subject
Dft Calculations
dc.subject.classification
Otras Ciencias Químicas
dc.subject.classification
Ciencias Químicas
dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
dc.title
Substituent-Modulated Conformation and Supramolecular Assembly of Tetronamides
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2018-07-18T20:50:23Z
dc.journal.volume
16
dc.journal.number
10
dc.journal.pagination
5798-5810
dc.journal.pais
Estados Unidos
dc.journal.ciudad
Washington
dc.description.fil
Fil: Karak, Milandip. Universidade Federal de Minas Gerais; Brasil. Universidade Federal de Viçosa; Brasil
dc.description.fil
Fil: Acosta, Jaime A. M.. Universidade Federal de Minas Gerais; Brasil
dc.description.fil
Fil: Barbosa, Luiz C. A.. Universidade Federal de Minas Gerais; Brasil. Universidade Federal de Viçosa; Brasil
dc.description.fil
Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
dc.description.fil
Fil: Da Silva, Cameron C.. Universidade Federal de Goiás; Brasil
dc.description.fil
Fil: Boukouvalas, John. Universite Laval; Francia
dc.description.fil
Fil: Martins, Felipe T.. Universidade Federal de Goiás; Brasil
dc.journal.title
Crystal Growth & Design
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/acs.cgd.6b00881
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.cgd.6b00881
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