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Volumn , Issue 10, 2009, Pages 1578-1584

Controlling selectivity for cycloadditions of nitrones and alkenes tethered by benzimidazoles: Combining experiment and theory

Author keywords

Cycloaddition; Nitrones; Quantum chemical calculations; Stereoselectivity; Substituent eff'ects; Transition states

Indexed keywords


EID: 64549098066     PISSN: 1434193X     EISSN: 10990690     Source Type: Journal    
DOI: 10.1002/ejoc.200801211     Document Type: Article
Times cited : (9)

References (58)
  • 1
    • 23044431676 scopus 로고    scopus 로고
    • For leading references on intramolecular dipolar cycloadditions, see: a
    • For leading references on intramolecular dipolar cycloadditions, see: a) I. Coldham, R. Hufton, Chem. Rev. 2005, 105, 2765-2810;
    • (2005) Chem. Rev , vol.105 , pp. 2765-2810
    • Coldham, I.1    Hufton, R.2
  • 7
    • 64549139464 scopus 로고    scopus 로고
    • Closely related systems: a with tether imidazole, R1, R 2, R3, II, R4, Bn or phenylethyl: E. Beccalli, G. Broggini, A. Contini, I. De Marchi, G. Zecchi, C. Zoni, Tetrahedron: Asymmetry 2004, 15, 3181-3187 (gas phase MP2/6-31 1++G**//HF/6-31G** and MP2/6-31+G**//HF/6-31G** calculations were reported for two systems in this paper) and D. Basso, G. Broggini, D. Passarella, T. Pilati, A. Terraneo, G. Zecchi, Tetrahedron 2002, 58, 4445-4450 [consistent with our results (see Table 1, product A predominated for the two examples reported therein without additional allylic substituents, b) with tether pyrrole or butylpyrrole, R1, H, Me, Pr, Ph, R2, H, Me, R3, H, R4, Bn, phenylethyl: G. Broggini, C. La Rosa, T. Pilati, A. Terraneo, G. Zecchi, Tetrahedron 2001, 57, 8323-8332: A. Arnone, G
    • 3 = H led to product A as the major product];
  • 8
    • 0034731631 scopus 로고    scopus 로고
    • with tether indole, R1, Ph, R2, H, R 3, H, R4, H, Bn, phenylethyl: E. M. Beccalli, G. Broggini, C. La Rosa, D. Passarella, T. Pilati, A. Terraneo. G. Zecchi, J. Org. Chem. 2000, 65, 8924-8932 [consistent with our results see Table 1, for the two cases reported therein with R1, R 2, R3, H, product A was the major product, and for the two cases with R1, Ph, product B was the major product, Note that with a 3-methylindole tether, products of type B were reported for R1= R2, R3, H; see: D. St. C. Black, D. C. Craig, R. B. Deb-Das. N. Kumar. Aust. J. Chem. 1993, 46. 603-622
    • 3 = H; see: D. St. C. Black, D. C. Craig, R. B. Deb-Das. N. Kumar. Aust. J. Chem. 1993, 46. 603-622:
  • 11
    • 0036310112 scopus 로고    scopus 로고
    • in these cases, only products of type B were observed: For systems with cyclohexenes directly attached to the N of a pyrrole or indole tether, see
    • e) For systems with cyclohexenes directly attached to the N of a pyrrole or indole tether, see: E. M. Beccalli, G. Broggini. A. Farina, L. Malpezzi, A. Terraneo. G. Zecchi. Eur. J. Org. Chem. 2002, 2080-2086; in these cases, only products of type B were observed:
    • (2002) Eur. J. Org. Chem , pp. 2080-2086
    • Beccalli, E.M.1    Broggini, G.2    Farina, A.3    Malpezzi, L.4    Terraneo, A.5    Zecchi, G.6
  • 12
    • 53849124721 scopus 로고    scopus 로고
    • -)Bn attached to N and a vinyl group attached to carbonj, see: E. Borsini, G. Broggini. A. Contini, G. Zecchi, Eur. J. Org. Chem. 2008, 2808-2816.
    • -)Bn attached to N and a vinyl group attached to carbonj, see: E. Borsini, G. Broggini. A. Contini, G. Zecchi, Eur. J. Org. Chem. 2008, 2808-2816.
  • 14
    • 36849090099 scopus 로고    scopus 로고
    • For our work on related cycloadditions using azomethine ylides, see
    • a) For our work on related cycloadditions using azomethine ylides, see: L. Meng, J. C. Fettinger, M. J. Kurth. Org. Lett. 2007, 9, 5055-5058;
    • (2007) Org. Lett , vol.9 , pp. 5055-5058
    • Meng, L.1    Fettinger, J.C.2    Kurth, M.J.3
  • 15
    • 64549112326 scopus 로고    scopus 로고
    • A 36 compound collection of the heterocycles reported in this manuscript has been added to the NIH Molecular Libraries Small Molecule Repository (MLSMR) for high-throughput biological screening.
    • b) A 36 compound collection of the heterocycles reported in this manuscript has been added to the NIH Molecular Libraries Small Molecule Repository (MLSMR) for high-throughput biological screening.
  • 16
    • 64549096130 scopus 로고    scopus 로고
    • Experimental and computational details can be found in the Supporting Information. |8J This is true even though the computed energies are for gas phase calculations. Tests on selected systems indicated that solvation (modeled using a continuum approach) has only small effects on the relative energies of the transition-state structures. See Supporting Information for details.
    • Experimental and computational details can be found in the Supporting Information. |8J This is true even though the computed energies are for gas phase calculations. Tests on selected systems indicated that solvation (modeled using a continuum approach) has only small effects on the relative energies of the transition-state structures. See Supporting Information for details.
  • 20
    • 64549148113 scopus 로고    scopus 로고
    • I. S. Kim, G. R. Dong, Y. II. lung, J. Org. Chem. 2007, 72, 5424-5426.
    • I. S. Kim, G. R. Dong, Y. II. lung, J. Org. Chem. 2007, 72, 5424-5426.
  • 29
    • 0344116747 scopus 로고
    • Ed, B. S. Thyagarajan, Interscience Publishers, New York
    • M. Lamchen, in Mechanisms of Molecular Migrations (Ed.: B. S. Thyagarajan), Interscience Publishers, New York, 1968, vol. 1, pp. 1-60.
    • (1968) Mechanisms of Molecular Migrations , vol.1 , pp. 1-60
    • Lamchen, M.1
  • 30
    • 64549129703 scopus 로고    scopus 로고
    • Note also that no correlation was observed between the computed preference of a given nitrone for the E or Zgeometry and the experimentally observed preference for a particular cycloaddition product. See Supporting Information for details on computed nitrone structures. Note also that for cases where nitrone products were observed (i.e, cycloaddition did not occur, mixtures of geometric isomers were observed when R4, Me but only one geometric isomer (of unknown stereochemistry) was observed when R 4, cHex
    • 4 = cHex.
  • 31
    • 1542554559 scopus 로고
    • For a review, see
    • For a review, see: J. I. Seeman, Chem. Rev. 1983, 83, 83-134.
    • (1983) Chem. Rev , vol.83 , pp. 83-134
    • Seeman, J.I.1
  • 32
    • 64549121241 scopus 로고    scopus 로고
    • Solvation 'single point calculations [CPCM(UAKS)-B3IYP/6-31G(d) using water] were also carried out, and these barriers do not change significantly. See Supporting Information for details;
    • a) Solvation 'single point calculations [CPCM(UAKS)-B3IYP/6-31G(d) using water] were also carried out, and these barriers do not change significantly. See Supporting Information for details;
  • 33
    • 64549147669 scopus 로고    scopus 로고
    • We are aware that the presence of the benzimidazole ring could significantly lower these barriers, but we have as yet been unable to locate analogous transition-state structures using larger models that include benzimidazole rings
    • b) We are aware that the presence of the benzimidazole ring could significantly lower these barriers, but we have as yet been unable to locate analogous transition-state structures using larger models that include benzimidazole rings.
  • 34
    • 64549148586 scopus 로고    scopus 로고
    • [25c] of these nitrones were used to make these ZIE assignments (data presented in the Supporting Information);
    • [25c] of these nitrones were used to make these ZIE assignments (data presented in the Supporting Information);
  • 35
    • 64549099108 scopus 로고    scopus 로고
    • [25c] (data presented in the Supporting Information);
    • [25c] (data presented in the Supporting Information);
  • 37
    • 64549093466 scopus 로고    scopus 로고
    • Note that reaction of the nitrone with 1-pentyne did not lead to any cycloadduct, consistent with the results described earlier for systems with tethered alkynes
    • Note that reaction of the nitrone with 1-pentyne did not lead to any cycloadduct, consistent with the results described earlier for systems with tethered alkynes.
  • 38
    • 33747239619 scopus 로고    scopus 로고
    • This is an example of torsional steering. For leading references, see: R. G. lafe, K. N. Houk, Org. Lett. 2006, 8, 3469-3472
    • This is an example of "torsional steering". For leading references, see: R. G. lafe, K. N. Houk, Org. Lett. 2006, 8, 3469-3472.
  • 39
    • 64549155806 scopus 로고    scopus 로고
    • [59.30] but no desired cycloadduct was obtained.
    • [59.30] but no desired cycloadduct was obtained.
  • 42
    • 44349105904 scopus 로고    scopus 로고
    • For leading references on microwave heating, see: a
    • For leading references on microwave heating, see: a) CO. Kappe, Chem. Soc. Rev. 2008, 37, 1 127-1139;
    • (2008) Chem. Soc. Rev , vol.37 , Issue.1 , pp. 127-1139
    • Kappe, C.O.1
  • 45
    • 64549089085 scopus 로고    scopus 로고
    • Gaussian 03, revision B.04, Gaussian, Inc., Pittsburgh, PA, 2004 (see Supporting Information for the full citation including all author names).
    • Gaussian 03, revision B.04, Gaussian, Inc., Pittsburgh, PA, 2004 (see Supporting Information for the full citation including all author names).
  • 50
    • 27744489233 scopus 로고    scopus 로고
    • The reliability of the B3I.YP/6-31 G(d) method for modeling dipolar cycloaddition reactions has been assessed previously. See, for example: D. II. Ess, K. N. Houk, J. Phys. Chem. A 2005, 109, 9542-9553:
    • e) The reliability of the B3I.YP/6-31 G(d) method for modeling dipolar cycloaddition reactions has been assessed previously. See, for example: D. II. Ess, K. N. Houk, J. Phys. Chem. A 2005, 109, 9542-9553:
  • 58
    • 64549127483 scopus 로고    scopus 로고
    • N. Müller, A. Falk, Ball & Stick V.3.7.6, molecular graphics application for MacOS computers, Johannes Kepler University. Linz, 2000.
    • N. Müller, A. Falk, Ball & Stick V.3.7.6, molecular graphics application for MacOS computers, Johannes Kepler University. Linz, 2000.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.