Soto-Delgado, J.; Sáez-Cases, JA.; Tapia, RA.; Domingo, LR. (2013). Theoretical study on the molecular mechanism of the [5 + 2] vs. [4 + 2] cyclization mediated by Lewis acid in the quinone system. Organic and Biomolecular Chemistry. 11(48):8357-8365. doi:10.1039/c3ob41860j
Por favor, use este identificador para citar o enlazar este ítem: http://hdl.handle.net/10251/85252
Title:
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Theoretical study on the molecular mechanism of the [5 + 2] vs. [4 + 2] cyclization mediated by Lewis acid in the quinone system
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Author:
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Soto-Delgado, Jorge
Sáez-Cases, José Antonio
Tapia, Ricardo A.
Domingo, Luis R.
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UPV Unit:
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Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química
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Issued date:
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Abstract:
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[EN] The thermal and Lewis acid (LA) catalyzed cyclizations of quinone 1 involved in the synthesis of Colombiasin A and Elipsaterosin B have been theoretically studied using DFT methods at the B3LYP/6-311G(d,p) computational ...[+]
[EN] The thermal and Lewis acid (LA) catalyzed cyclizations of quinone 1 involved in the synthesis of Colombiasin A and Elipsaterosin B have been theoretically studied using DFT methods at the B3LYP/6-311G(d,p) computational level. B3LYP calculations suggest that the formal endo [4 + 2] cycloadduct allowing the synthesis of Colombiasin A is preferentially formed under thermal conditions, while in the presence of the BF3 LA catalyst the formal [5 + 2] cycloadduct is seen, allowing the synthesis of Elipsaterosin B. The BF3 LA catalyst not only accelerates the nucleophilic attack on the C2 carbon of the quinone framework through a more polar C-C bond formation, but also provokes a different electron density rearrangement along the nucleophilic attack favoring the subsequent C-C bond formation at the C4 carbon with the formation of the formal [5 + 2] cycloadduct. ELF bonding analysis along these cyclizations indicates that the C-C single bond formation takes place in the range of 1.91-2.1 angstrom by C-to-C coupling of two pseudoradical centers. Along the formation of the first C2-C9 single bond, these pseudoradical centers appear at one of the most electrophilic and at one of the most nucleophilic centers of quinone 1, C2 and C9 carbons, respectively. Analysis of the Parr functions suggests that although the most favorable electrophilic/nucleophilic interaction is that involving the C2 carbon of quinone and the C12 carbon of the butadiene framework, the intramolecular nature of the cyclization prevents the corresponding reactive channel.
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Subjects:
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Electron localization function
,
Polarizable continuum model
,
Diels-alder reaction
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Topological analysis
,
Bond formation
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Elf analysis
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Cycloaddition reaction
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(-) Elisapterosin-B
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(-) Colombiasin-A
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Copyrigths:
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Reserva de todos los derechos
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Source:
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Organic and Biomolecular Chemistry. (issn:
1477-0520
) (eissn:
1477-0539
)
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DOI:
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10.1039/c3ob41860j
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Publisher:
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Royal Society of Chemistry
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Publisher version:
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http://doi.org/10.1039/c3ob41860j
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Project ID:
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Ministerio de Economía, Fomento y Turismo, Chile/ICM-P10-003-F CILIS
FONDECYT/3130359
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Thanks:
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This work was supported by the Post-Doctoral fellow FONDECYT Grant 3130359 and Project ICM-P10-003-F CILIS granted by Fondo de Innovacion para la Competitividad del Ministerio de Economia, Fomento y Turismo, Chile.
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Type:
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Artículo
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