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According to Brandsma, "...it is difficult to obtain very pure 1,3-pentadiyne in a good yield using a safe isolation procedure." Brandsma, L. Preparative Acetylenic Chemistry, 2nd ed.; Elsevier: Amsterdam, 1988; p 45.
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15
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33644755153
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note
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The ketones 4a-c,e and dibromides 5b,c,e have been previously reported, others were synthesized by analogous routes. See Supporting Information for references as well as synthetic and spectroscopic details for all new compounds.
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16
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33644778294
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note
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The FBW rearrangement can be successfully accomplished in pure toluene, but product isolation is more difficult due to its higher boiling point. This is an issue in cases were the triyne product is not particularly stable to heating; a mixture of hexanes and toluene is procedurally the easiest.
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17
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33644757340
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note
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It is has not yet been established if deprotonation precedes the FBW rearrangement, or vice versa. Given the good yields of the reactions, however, the former seems more likely because the latter should lead to byproduct formation resulting from protonation of the carbenoid intermediate by the terminal acetylene.
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18
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84919123738
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and references therein
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A protocol for in situ formation and derivatization of 1-amino-di- and triynes has been reported. See: (a) Faul, D.; Himbert, G. Chem. Ber. 1988, 121, 1367-1369 and references therein.
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20
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0001677885
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For diynes, protocols exist for in situ acetylide formation and trapping. To our knowledge, these routes have not been generalized for triyne synthesis. For examples, see: (a) Negishi, E.; Okukado, N.; Lovich, S. F.; Luo, F.-T. J. Org. Chem. 1984, 49, 2629-2632.
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3242776187
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Otera and co-workers reported a double elimination method of β-substituted sulfones that addresses this problem. See: Ye, F.; Orita, A.; Yaruva, J.; Hamada, T.; Otera, J. Chem. Lett. 2004, 33, 528-529 and references therein.
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33
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In situ deprotection/coupling protocols can be quite effective. See, for example: Bell, M. L.; Chiechi, R. C.; Johnson, C. A.; Kimball, D. B.; Matzger, A. J.; Wan, W. B.; Weakley, T. J. R.; Haley, M. M. Tetrahedron 2001, 57, 3507-3520.
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Wan, W.B.6
Weakley, T.J.R.7
Haley, M.M.8
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35
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33644761513
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note
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The use of toluene rather than hexanes allows for higher reflux temperatures in the subsequent Negishi reaction.
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36
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33646120606
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41
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For zinc: (b) Negishi, E.; Bagheri, V.; Chatterjee, S.; Luo, F.-T.; Miller, J. A.; Stoll, A. T. Tetrahedron Lett. 1983, 24, 5181-5184.
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Palladium-catalyzed alkynylation of acyl halides with terminal alkynes has also been reported. See: Alonso, D. A.; Nájera, C.; Pacheco, M. C. J. Org. Chem. 2004, 69, 1615-1619 and references therein.
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