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1
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23044431676
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For leading references on intramolecular dipolar cycloadditions, see: a) I. Coldham, R. Hufton, Chem. Rev. 2005, 105, 2765-2810;
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B. G. Mullen, R. T. Decory. T. J. Mitchell, D. S. Allen, R. C. Kinsolving, J. Med. Chem. 1988, 31, 2008-2014.
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7
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64549139464
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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];
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-
-
-
8
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-
0034731631
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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
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3 = H; see: D. St. C. Black, D. C. Craig, R. B. Deb-Das. N. Kumar. Aust. J. Chem. 1993, 46. 603-622:
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-
-
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10
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34447523800
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For a system with a longer (anilinederived) tether, see
-
d) For a system with a longer (anilinederived) tether, see: G. Broggini, F. Colombo, I. De Marchi, S. Galli, M. Martinelli, G. Zecchi, Tetrahedron: Asymmetry 2007. 18, 1495-1501;
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(2007)
Tetrahedron: Asymmetry
, vol.18
, pp. 1495-1501
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Broggini, G.1
Colombo, F.2
De Marchi, I.3
Galli, S.4
Martinelli, M.5
Zecchi, G.6
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11
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0036310112
-
-
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
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12
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53849124721
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-)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.
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13
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0031549105
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M. A. Marx, A. L. Grillot, C. T. Louer, K. A. Beaver, P. A. Bartlett, J. Am. Chem. Soc. 1997, 119, 6153-6167.
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Bartlett, P.A.5
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14
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36849090099
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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;
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Meng, L.1
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15
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64549112326
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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.
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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.
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-
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16
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64549096130
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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.
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19
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0037453620
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C. Jimeno, M. Pasto, A. Riera, M. A. Pericas, J. Org. Chem. 2003, 65,3130-3138.
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I. S. Kim, G. R. Dong, Y. II. lung, J. Org. Chem. 2007, 72, 5424-5426.
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64549129703
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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.
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31
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For a review, see: J. I. Seeman, Chem. Rev. 1983, 83, 83-134.
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64549121241
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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;
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-
-
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33
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64549147669
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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
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[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
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[25c] (data presented in the Supporting Information);
-
[25c] (data presented in the Supporting Information);
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36
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0026598758
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c) H. G. Aurich, M. Franzke, H. P. Kesselheim, Tetrahedron 1992, 48, 663-668.
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Aurich, H.G.1
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37
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64549093466
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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.
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-
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38
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33747239619
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This is an example of torsional steering. For leading references, see: R. G. lafe, K. N. Houk, Org. Lett. 2006, 8, 3469-3472
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This is an example of "torsional steering". For leading references, see: R. G. lafe, K. N. Houk, Org. Lett. 2006, 8, 3469-3472.
-
-
-
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39
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64549155806
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[59.30] but no desired cycloadduct was obtained.
-
[59.30] but no desired cycloadduct was obtained.
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40
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64549089085
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Gaussian 03, revision B.04, Gaussian, Inc., Pittsburgh, PA, 2004 (see Supporting Information for the full citation including all author names).
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Gaussian 03, revision B.04, Gaussian, Inc., Pittsburgh, PA, 2004 (see Supporting Information for the full citation including all author names).
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27744489233
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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:
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N. Müller, A. Falk, Ball & Stick V.3.7.6, molecular graphics application for MacOS computers, Johannes Kepler University. Linz, 2000.
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