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0034536441
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33845557283
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1/2 = ca. I h). Kalwinsch, I.; Li, X.; Gottstein, J.; Huisgen, R. J. Am. Chem. Soc. 1981, 103, 7032.
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27
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0032488853
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note
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Padwa, A.; Price, A. T. J. Org. Chem. 1998, 63, 556 and 1995, 60, 6258. Interestingly, this endo diastereoselection is unique to the intramolecular 1,3-dipolar cycloaddition and intermolecular reactions proceed with indole exo cycloaddition directed to an analogous α-face, see: Muthusamy, S.; Gunanathan, C.; Babu, S. A. Tetrahedron Lett. 2001, 42, 523. The endo diastereoselection observed herein may be attributed simply to a conformational (strain) preference dictated by the dipolarophile tether since it mirrors the relative energy of the four possible products α-face endo < β-face endo ΔE = 5.2 kcal/mol < α-face exo ΔE = 13.1 kcal/mol < β-face exo ΔE = 151 kcal/mol for 14a, MM2 force field).
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28
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0010421175
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note
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Stereochemical assignments for 16b and 17b have been confirmed by X-ray of the analogous products bearing an indole C6 methoxy substitutent.
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29
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0010501363
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note
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The X-ray crystal structure of 21b has been deposited with the Cambridge Crystallographic Data Centre under the deposition number CCDC 186237.
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30
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0010421034
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note
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2 detection or isolation.
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33
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0010421315
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and refs cited therein
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For additional examples of allene > alkyne intramolecular Diels-Alders reactions, see: Kanematsu, K. Rev. Heteroat. Chem. 1993, 9, 213 and refs cited therein.
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Kanematsu, K.1
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