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1. For a discussion of strategy level reactions in synthesis design, see: Wender, P. A.; Miller, B. L. Toward the Ideal Synthesis: Connectivity Analysis and Multibond-Forming Processes. In Organic Synthesis: Theory and Applications; Hudlicky, T., Ed.; JAI Press: Greenwich, CT, 1993; Vol. 2, pp 27-66.
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2. For a method to circumvent this problem, see: Wender, P. A.; Correia, C. R. D. J. Am. Chem. Soc. 1987, 109, 2523-2525. For a lead reference on successful photo-induced [4 + 4] cycloadditions, see: Sieburth, S. McN.; Cunard, N. T. Tetrahedron 1996, 52, 6251-6282.
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2. For a method to circumvent this problem, see: Wender, P. A.; Correia, C. R. D. J. Am. Chem. Soc. 1987, 109, 2523-2525. For a lead reference on successful photo-induced [4 + 4] cycloadditions, see: Sieburth, S. McN.; Cunard, N. T. Tetrahedron 1996, 52, 6251-6282.
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For the original work on intramolecular diene-diene cycloadditions, see: (c) Wender, P. A.; Ihle, N. C. J. Am. Chem. Soc. 1986, 108, 4678-4679.
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For extensions to diene-allene cycloadditions and other metal catalysts, see: (i) Wender, P. A.; Jenkins, T. E.; Suzuki, S. J. Am. Chem. Soc. 1995, 117, 1843-1844.
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For extensions to homologous vinylcyclopropane-alkyne systems see: (j) Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc. 1995, 117, 4720-4721.
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0002110351
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4. Studies on metal catalyzed cycloadditions have been reported from several laboratories in recent years including those of Binger, Chiusoli, Davies, tom Dieck, Dötz, Furukawa, Grigg, Heimbach, Ito, Kreiter, Lautens, Liebeskind, Livinghouse, Matsuda, Mortreux, Motherwell, Nakamura, Negishi, Noyori, Ojima, Pirrung, Rigby, Sheridan, Smith, Stryker, Takacs, Trost, Tsuda, Tsuji, Vollhardt, Wulff, and Yamamoto. For lead references to these and related studies, see: (a) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49-92 and
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6. For the application of this process to diene-alkene systems, see: (a) Jolly, R. S.; Luedtke, G.; Sheehan, D.; Livinghouse, T. J. Am. Chem. Soc. 1990, 112, 4965-4966 and
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7. For representative reports of intermolecular [4 + 2] cycloadditions catalyzed by transition metals other than nickel, see: Iron: (a) tom Dieck, H.; Diercks, R. Angew. Chem. Int. Ed. Eng. 1983, 22, 778-779.
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0010708319
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note
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2 were also prepared, however the olefination procedure gave only trace amounts of the desired dienyne products in these cases.
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40
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41
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0010708320
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note
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3) and fluoro-(X = F) substituted dienynes were also prepared from the corresponding phosphonates in 67% and 44% yields, respectively. The nickel-catalyzed cycloadditions of these substrates both proceeded in 73% yield.
-
-
-
-
42
-
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0010658890
-
-
note
-
3C- and F-substituted dienynes were completely unaffected by prolonged heating at 250 °C.
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-
43
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0010743104
-
-
note
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24. The rates of cycloaddition of the trifluoromethyl- and fluoro-substituted dienynes relative to the unsubstituted case were measured to be 0.75 and 0.63, respectively.
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45
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note
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4-diene also would explain this conservation of stereochemistry. The observed reactivity differences for the methyl-substituted stubstrates, however, are less easly accommodated by such a model.
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52
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1H NMR with a characteristic trans coupling constant of 13.7 Hz.
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