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Volumn 72, Issue 20, 2007, Pages 7656-7666

Experimental and DFT studies on competitive heterocyclic rearrangements. Part 2: A one-atom side-chain versus the classic three-atom side-chain (Boulton-Katritzky) ring rearrangement of 3-acylamino-1,2,4-oxadiazoles

Author keywords

[No Author keywords available]

Indexed keywords

HIGH TEMPERATURE EFFECTS; MOLECULAR INTERACTIONS; ORGANIC COMPOUNDS;

EID: 34848848436     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo701306t     Document Type: Article
Times cited : (33)

References (90)
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    • For Part 1, see: Pace, A.; Buscemi, S.; Vivona, N.; Silvestri, A.; Barone, G. J. Org. Chem. 2006, 71, 2740-2749.
    • For Part 1, see: Pace, A.; Buscemi, S.; Vivona, N.; Silvestri, A.; Barone, G. J. Org. Chem. 2006, 71, 2740-2749.
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    • See also specific classes of ring transformations reviewed in: (e) Comprehensive Heterocyclic Chemistry; Katritzky, A. R., Rees, C. W., Eds; Pergamon Press: Oxford, 1984; Vols. 1-8.
    • See also specific classes of ring transformations reviewed in: (e) Comprehensive Heterocyclic Chemistry; Katritzky, A. R., Rees, C. W., Eds; Pergamon Press: Oxford, 1984; Vols. 1-8.
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    • Katritzky, A. R, Rees, C. W, Scriven, E. F. V, Eds; Elsevier: Amsterdam, Vols
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    • Katritzky, A. R, Rees, C. W, Eds; Pergamon Press: Oxford
    • (b) Comprehensive Heterocyclic Chemistry; Katritzky, A. R., Rees, C. W., Eds; Pergamon Press: Oxford, 1984; Vol. 1.
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    • For recent mechanistic studies on azole-to-azole interconversion reactions of the Boulton-Katritzky type, see: (a) Cosimelli, B, Guernelli, S, Spinelli, D, Buscemi, S, Frenna, V, Macaluso, G. J. Org. Chem. 2001, 66, 6124-6129
    • For recent mechanistic studies on azole-to-azole interconversion reactions of the Boulton-Katritzky type, see: (a) Cosimelli, B.; Guernelli, S.; Spinelli, D.; Buscemi, S.; Frenna, V.; Macaluso, G. J. Org. Chem. 2001, 66, 6124-6129.
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    • Moreover, for DFT studies on bicyclic BKR, see for example: (g) Eckert, F.; Rauhut, G. J. Am. Chem. Soc. 1998, 120, 13478-13484.
    • Moreover, for DFT studies on bicyclic BKR, see for example: (g) Eckert, F.; Rauhut, G. J. Am. Chem. Soc. 1998, 120, 13478-13484.
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    • (h) Rauhut, G. J. Org. Chem. 2001, 66, 5444-5448.
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    • 6b,c,e Moreover, copper(II) acetate catalysis has been reported for the BKR of some arylhydrazones of 3-benzoyl-1-oxa-2-azoles. Buscemi, S.; Frenna, V.; Vivona, N.; Spinelli, D. J. Chem. Soc., Perkin Trans. 1 1993, 2491-2493.
    • 6b,c,e Moreover, copper(II) acetate catalysis has been reported for the BKR of some arylhydrazones of 3-benzoyl-1-oxa-2-azoles. Buscemi, S.; Frenna, V.; Vivona, N.; Spinelli, D. J. Chem. Soc., Perkin Trans. 1 1993, 2491-2493.
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    • (S) 1985, 190.
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    • 8c See also: (a) Baryshnikova, E. L.; Kulikov, A. S.; Ovchinnikov, I. V.; Solomentsev, V. S.; Makhova, N. N. Mendeleev Commun. 2001, 230-232.
    • 8c See also: (a) Baryshnikova, E. L.; Kulikov, A. S.; Ovchinnikov, I. V.; Solomentsev, V. S.; Makhova, N. N. Mendeleev Commun. 2001, 230-232.
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    • For a similar rearrangement leading to a 5-trifluoromethylisoxazole, see: Sumimoto, S.; Ishizuka, I.; Ueda, S; Takase, A.; Okuno, K. Jpn. Patent 01009978, 1989; Chem. Abstr. 1989, 111, 57722.
    • For a similar rearrangement leading to a 5-trifluoromethylisoxazole, see: Sumimoto, S.; Ishizuka, I.; Ueda, S; Takase, A.; Okuno, K. Jpn. Patent 01009978, 1989; Chem. Abstr. 1989, 111, 57722.
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    • 10c See also: (a) Andrianov, V. G.; Semenikhina, V. G.; Eremeev, A. V.; Gaukhman, A. P. Chem. Heterocycl. Compd. (Engl. Transl.) 1988, 24, 1410.
    • 10c See also: (a) Andrianov, V. G.; Semenikhina, V. G.; Eremeev, A. V.; Gaukhman, A. P. Chem. Heterocycl. Compd. (Engl. Transl.) 1988, 24, 1410.
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    • A = 48. (a) Bird, C. V. Tetrahedron 1985, 41, 1409-1414.
    • A = 48. (a) Bird, C. V. Tetrahedron 1985, 41, 1409-1414.
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    • For photoinduced rearrangements involving the 1,2,4-oxadiazole heterocycle, see: a, and references cited therein
    • For photoinduced rearrangements involving the 1,2,4-oxadiazole heterocycle, see: (a) Vivona, N.; Buscemi, S. Heterocycles 1995, 41, 2095-2116 and references cited therein.
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    • 2d (Addition of a Nucleophile Ring-Opening Ring-Closure) rearrangements of 1,2,4-oxadiazoles see: (a) Buscemi, S.; Pace, A.; Palumbo Piccionello, A.; Macaluso, G.; Vivona, N.; Spinelli, D.; Giorgi, G. J. Org. Chem. 2005, 70, 3288-3291.
    • 2d (Addition of a Nucleophile Ring-Opening Ring-Closure) rearrangements of 1,2,4-oxadiazoles see: (a) Buscemi, S.; Pace, A.; Palumbo Piccionello, A.; Macaluso, G.; Vivona, N.; Spinelli, D.; Giorgi, G. J. Org. Chem. 2005, 70, 3288-3291.
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    • Higher temperatures were used for a short experimental time during a dynamic NMR study on the BKR of the anion of 3-acetylamino-5-methyl-1,2,4- oxadiazole 29a.15a
    • 15a
  • 74
    • 34848817521 scopus 로고    scopus 로고
    • - anions (see Figure 2). However, in that occasion, due to the short time spent at 112°C, the low resolution of NMR spectra, and the extended exchange of the methyl protons with DMSO deuteria, no further rearrangement was detected.
    • - anions (see Figure 2). However, in that occasion, due to the short time spent at 112°C, the low resolution of NMR spectra, and the extended exchange of the methyl protons with DMSO deuteria, no further rearrangement was detected.
  • 75
    • 34848872643 scopus 로고    scopus 로고
    • An analytical reaction performed on representative 29a in DMSO/t-BuOK gave comparable results to those obtained in DMF. Therefore, although preparative scale reactions described in this article have been performed in DMF, we chose to use the available DMSO model solvent to mimic the polar aprotic solvent media in our computational study
    • An analytical reaction performed on representative 29a in DMSO/t-BuOK gave comparable results to those obtained in DMF. Therefore, although preparative scale reactions described in this article have been performed in DMF, we chose to use the available DMSO model solvent to mimic the polar aprotic solvent media in our computational study.
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    • In a previous paper,1 we pointed out the possibility of a thermal equilibrium to occur between the diazirine B (formed through a migration step from oxadiazole A) and the diazirine C originated through a ring-contraction step from oxadiazole A, Chemical Equation Presented
    • 1 we pointed out the possibility of a thermal equilibrium to occur between the diazirine B (formed through a migration step from oxadiazole A) and the diazirine C (originated through a ring-contraction step from oxadiazole A). (Chemical Equation Presented)
  • 77
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    • An accurate determination of the anionic BKR equilibrium 33, ⇆ 36- composition would require a higher base/substrate ratio to guarantee for complete deprotonation of the starting oxadiazole.15d However, the use of t-BuOK/oxadiazole ratios higher than 0.5 in DMSO-d6 was not achievable because of low solubility of the formed salts. Moreover, an even lower solubility of these salts was observed when DMF-d7 was used
    • 7 was used.
  • 78
    • 34848858364 scopus 로고    scopus 로고
    • Calculations on anions 33- and 36- in MeOH showed anion 33- being 0.5 kJ/mol more stable than 36, in good agreement with the experimentally determined equilibrium composition in CD3OD.15d On the other hand, due to the experimental difficulties encountered,26 a rigorous comparison between the experimental and computational data is not possible in the case of BKR equilibrium 33- ⇆ 36- in DMSO for which the little discordance about the stability order is within the numerical accuracy of the computational method. In our opinion, only the explicit consideration of coordinating solvent molecules in our DFT calculation, in addition to the PCM approach, could in this isolated case reproduce the stability order, experimentally determined
    • - in DMSO for which the little discordance about the stability order is within the numerical accuracy of the computational method. In our opinion, only the explicit consideration of coordinating solvent molecules in our DFT calculation, in addition to the PCM approach, could in this isolated case reproduce the stability order, experimentally determined.
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