Supramolecular catalysis at work: Diastereoselective synthesis of a molecular bowl with dynamic inner space
Само за регистроване кориснике
2008
Аутори
Yan, ZhiqingMcCracken, Troy
Xia, Shijing
Maslak, Veselin
Gallucci, Judith
Hadad, Christopher M.
Bađić, Jovica D.
Чланак у часопису (Објављена верзија)
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Приказ свих података о документуАпстракт
[GRAPHICS] The supramolecular assistance to Pd(0)/Cu(I)-catalyzed cyclotrimerization of stannylated norbornene 7 has been investigated to give molecular bowl 1(syn) in a stereoselective fashion. Following a divergent strategy, racemic norbornene 7 was synthesized in satisfactory yield. Self-coupling, promoted by Pd(0)/Cu(I) catalysis acting in synergy with CsF, yielded molecular bowl 1(syn) in a moderate 30% yield. The reaction diastereoselectivity is affected by the concentration of Cu(I) and Cs+: increasing quantities of the cations enhanced the synlanti ratio of the isolated cyclotrimer from statistical (1:3) to a more desirable (4.5:1) ratio, in favor of the molecular bowl 1(syn) H-1 NMR spectroscopic studies suggested the coordinating affinity of 1(syn) toward transition metals Cu(I), Ag(I), and Au(I), to account for the observed templation effect. In particular, the tridentate 1(syn) has been shown to bind to one Ag(I) cation in the assembly process that is driven with enthalpy (...Delta H-0 = - 19 +/- 2 kcal/mol, Delta S-0 = -45 eu). The complete coordination was not cooperative, and was hypothesized to be impeded with the adverse entropy. Accordingly, density functional theory (BP86) calculations of 1(syn) and its mono-, bis-, and tris-Ag(I) complexes suggested that the coordination of one to three silver cations is highly exothermic. The calculations also revealed that the bowl constriction is necessary for the aromatic arms to become preorganized and bind to a silver cation(s) (Delta E approximate to 8 kcal/mol). Ultimately, Ag(I) has been shown to assist the diastereoselective formation of lending support to the notion, of template-directed synthesis.
Извор:
Journal of Organic Chemistry, 2008, 73, 2, 355-363Издавач:
- Amer Chemical Soc, Washington
DOI: 10.1021/jo701538g
ISSN: 0022-3263
PubMed: 17929868
WoS: 000252325200001
Scopus: 2-s2.0-40949152778
Колекције
Институција/група
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Yan, Zhiqing AU - McCracken, Troy AU - Xia, Shijing AU - Maslak, Veselin AU - Gallucci, Judith AU - Hadad, Christopher M. AU - Bađić, Jovica D. PY - 2008 UR - https://cherry.chem.bg.ac.rs/handle/123456789/899 AB - [GRAPHICS] The supramolecular assistance to Pd(0)/Cu(I)-catalyzed cyclotrimerization of stannylated norbornene 7 has been investigated to give molecular bowl 1(syn) in a stereoselective fashion. Following a divergent strategy, racemic norbornene 7 was synthesized in satisfactory yield. Self-coupling, promoted by Pd(0)/Cu(I) catalysis acting in synergy with CsF, yielded molecular bowl 1(syn) in a moderate 30% yield. The reaction diastereoselectivity is affected by the concentration of Cu(I) and Cs+: increasing quantities of the cations enhanced the synlanti ratio of the isolated cyclotrimer from statistical (1:3) to a more desirable (4.5:1) ratio, in favor of the molecular bowl 1(syn) H-1 NMR spectroscopic studies suggested the coordinating affinity of 1(syn) toward transition metals Cu(I), Ag(I), and Au(I), to account for the observed templation effect. In particular, the tridentate 1(syn) has been shown to bind to one Ag(I) cation in the assembly process that is driven with enthalpy (Delta H-0 = - 19 +/- 2 kcal/mol, Delta S-0 = -45 eu). The complete coordination was not cooperative, and was hypothesized to be impeded with the adverse entropy. Accordingly, density functional theory (BP86) calculations of 1(syn) and its mono-, bis-, and tris-Ag(I) complexes suggested that the coordination of one to three silver cations is highly exothermic. The calculations also revealed that the bowl constriction is necessary for the aromatic arms to become preorganized and bind to a silver cation(s) (Delta E approximate to 8 kcal/mol). Ultimately, Ag(I) has been shown to assist the diastereoselective formation of lending support to the notion, of template-directed synthesis. PB - Amer Chemical Soc, Washington T2 - Journal of Organic Chemistry T1 - Supramolecular catalysis at work: Diastereoselective synthesis of a molecular bowl with dynamic inner space VL - 73 IS - 2 SP - 355 EP - 363 DO - 10.1021/jo701538g ER -
@article{ author = "Yan, Zhiqing and McCracken, Troy and Xia, Shijing and Maslak, Veselin and Gallucci, Judith and Hadad, Christopher M. and Bađić, Jovica D.", year = "2008", abstract = "[GRAPHICS] The supramolecular assistance to Pd(0)/Cu(I)-catalyzed cyclotrimerization of stannylated norbornene 7 has been investigated to give molecular bowl 1(syn) in a stereoselective fashion. Following a divergent strategy, racemic norbornene 7 was synthesized in satisfactory yield. Self-coupling, promoted by Pd(0)/Cu(I) catalysis acting in synergy with CsF, yielded molecular bowl 1(syn) in a moderate 30% yield. The reaction diastereoselectivity is affected by the concentration of Cu(I) and Cs+: increasing quantities of the cations enhanced the synlanti ratio of the isolated cyclotrimer from statistical (1:3) to a more desirable (4.5:1) ratio, in favor of the molecular bowl 1(syn) H-1 NMR spectroscopic studies suggested the coordinating affinity of 1(syn) toward transition metals Cu(I), Ag(I), and Au(I), to account for the observed templation effect. In particular, the tridentate 1(syn) has been shown to bind to one Ag(I) cation in the assembly process that is driven with enthalpy (Delta H-0 = - 19 +/- 2 kcal/mol, Delta S-0 = -45 eu). The complete coordination was not cooperative, and was hypothesized to be impeded with the adverse entropy. Accordingly, density functional theory (BP86) calculations of 1(syn) and its mono-, bis-, and tris-Ag(I) complexes suggested that the coordination of one to three silver cations is highly exothermic. The calculations also revealed that the bowl constriction is necessary for the aromatic arms to become preorganized and bind to a silver cation(s) (Delta E approximate to 8 kcal/mol). Ultimately, Ag(I) has been shown to assist the diastereoselective formation of lending support to the notion, of template-directed synthesis.", publisher = "Amer Chemical Soc, Washington", journal = "Journal of Organic Chemistry", title = "Supramolecular catalysis at work: Diastereoselective synthesis of a molecular bowl with dynamic inner space", volume = "73", number = "2", pages = "355-363", doi = "10.1021/jo701538g" }
Yan, Z., McCracken, T., Xia, S., Maslak, V., Gallucci, J., Hadad, C. M.,& Bađić, J. D.. (2008). Supramolecular catalysis at work: Diastereoselective synthesis of a molecular bowl with dynamic inner space. in Journal of Organic Chemistry Amer Chemical Soc, Washington., 73(2), 355-363. https://doi.org/10.1021/jo701538g
Yan Z, McCracken T, Xia S, Maslak V, Gallucci J, Hadad CM, Bađić JD. Supramolecular catalysis at work: Diastereoselective synthesis of a molecular bowl with dynamic inner space. in Journal of Organic Chemistry. 2008;73(2):355-363. doi:10.1021/jo701538g .
Yan, Zhiqing, McCracken, Troy, Xia, Shijing, Maslak, Veselin, Gallucci, Judith, Hadad, Christopher M., Bađić, Jovica D., "Supramolecular catalysis at work: Diastereoselective synthesis of a molecular bowl with dynamic inner space" in Journal of Organic Chemistry, 73, no. 2 (2008):355-363, https://doi.org/10.1021/jo701538g . .