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43249089367
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During the preparation of our manuscript, Matsubara and co-workers reported a nickel-catalyzed decarbonylative alkyne insertion of phthalimides: Kajita, Y.; Matsubara, S.; Kurahashi, T J. Am. Chem. Soc. 2008, 130, 6058.
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(f) During the preparation of our manuscript, Matsubara and co-workers reported a nickel-catalyzed decarbonylative alkyne insertion of phthalimides: Kajita, Y.; Matsubara, S.; Kurahashi, T J. Am. Chem. Soc. 2008, 130, 6058.
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For thermolysis of 3-aryl-1,2,3-benzotriazin-4(3H)-ones, see: (a) Hey, D. H.; Rees, C. W.; Todd, A. R. J Chem. Soc. C 1968, 1028.
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24
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0037042297
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For precedence of an intermediacy of a similar azanickelacycle, see: a
-
For precedence of an intermediacy of a similar azanickelacycle, see: (a) Takahashi, T.; Tsai, F.-Y.; Li, Y.; Wang, H.; Kondo, Y.; Yamanaka, M.; Nakajima, K.; Kotora, M. J. Am. Chem. Soc. 2002, 124, 5059.
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27
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28244462079
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For a previous example of alkyne insertion into a related seven-membered ring nickelacycle intermediate, see: Korivi, R. P, Cheng, C.-H. Org. Lett. 2005, 7, 5179. The authors assumed that a carbon-carbon triple bond can insert into both carbon-nickel and nitrogen-nickel linkages depending on alkynes. The regiochemistry observed in the present reaction using ethyl hex-2-ynoate (2h) suggests that a carbon-nickel linkage react with 2h. In the reaction of other alkynes such as terminal alkynes, however, insertion into a nitrogen-nickel linkage cannot be ruled out
-
For a previous example of alkyne insertion into a related seven-membered ring nickelacycle intermediate, see: Korivi, R. P.; Cheng, C.-H. Org. Lett. 2005, 7, 5179. The authors assumed that a carbon-carbon triple bond can insert into both carbon-nickel and nitrogen-nickel linkages depending on alkynes. The regiochemistry observed in the present reaction using ethyl hex-2-ynoate (2h) suggests that a carbon-nickel linkage react with 2h. In the reaction of other alkynes such as terminal alkynes, however, insertion into a nitrogen-nickel linkage cannot be ruled out.
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28
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59949084352
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The benzotriazinone 1g was recovered.
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The benzotriazinone 1g was recovered.
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29
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59949100534
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See the Supporting Information for details
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See the Supporting Information for details.
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30
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59949099908
-
-
Although a similar regiochemical preference was explained by assuming stabilization of a partial negative charge on the carbon α to nickel in ref 9b, the effect of the aryl substituent observed with the present reaction is inconsistent with this explanation. Further studies including a theoretical one are necessary for elucidation of the mechanistic and regiochemical issue
-
Although a similar regiochemical preference was explained by assuming stabilization of a partial negative charge on the carbon α to nickel in ref 9b, the effect of the aryl substituent observed with the present reaction is inconsistent with this explanation. Further studies including a theoretical one are necessary for elucidation of the mechanistic and regiochemical issue.
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31
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59949104314
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3 was self-oligomerization of 2h.
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3 was self-oligomerization of 2h.
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32
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9444224982
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For examples of the regioselective formation of α-boryl-substituted metalacycle intermediates, see: (a) Quntar, A. A. A, Srebnik, M. Org. Lett. 2004, 6, 4243
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For examples of the regioselective formation of α-boryl-substituted metalacycle intermediates, see: (a) Quntar, A. A. A.; Srebnik, M. Org. Lett. 2004, 6, 4243.
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(c) Nishihara, Y.; Miyasaka, M.; Okamoto, M.; Takahashi, H.; Inoue, E.; Tanemura, K.; Takagi, K. J. Am. Chem. Soc. 2007, 129, 12634.
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35
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36
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33845185445
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For a similar stabilization by a silyl substituent, see
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For a similar stabilization by a silyl substituent, see: Buchwald, S. L.; Nielsen, R. B. J. Am. Chem. Soc. 1989, 111, 2870.
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37
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59949092686
-
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3 (85:15), DPPPen (92: 8), DPEphos (88:12), XANTPHOS (93:7).
-
3 (85:15), DPPPen (92: 8), DPEphos (88:12), XANTPHOS (93:7).
-
-
-
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38
-
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59949094501
-
-
3 as the ligand. For example, the reaction of 1-phenylprop-1-yne using dppf required heating at 80°C in toluene, giving inferior regioselectivity of 65:35.
-
3 as the ligand. For example, the reaction of 1-phenylprop-1-yne using dppf required heating at 80°C in toluene, giving inferior regioselectivity of 65:35.
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