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Only a handful of examples of the synthesis of N-unprotected indoles by intermolecular C-H annulation with alkynes have been reported; see Refs. [3g, 7l,o,q].
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The high KIE values (2.6-4.0) observed in this reaction suggest that slow hydrogen abstraction might occur after the electrophilic attack of Rh on the N-phenyl ring in the C-H activation process. For similar observations, see Ref. [13]; see also.
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The high KIE values (2.6-4.0) observed in this reaction suggest that slow hydrogen abstraction might occur after the electrophilic attack of Rh on the N-phenyl ring in the C-H activation process. For similar observations, see Ref. [13]; see also:, X. Zhao, C. S. Yeung, V. M. Dong, J. Am. Chem. Soc. 2010, 132, 5837.
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With 0.25 equivalents of [{CpRhCl2}2] (50 mol % Rh), 4 a was isolated in 35 % yield, and no 3 a was detected.
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With 0.25 equivalents of [{CpRhCl2}2] (50 mol % Rh), 4 a was isolated in 35 % yield, and no 3 a was detected.
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Use of Fe(OAc)2 or Mn(OAc)2 (1 equiv) instead of Cu(OAc)2 did not afford any product. The replacement of Cu(OAc)2 with Cu(OTf)2 (1 equiv) only gave 3 a in 30 % yield.
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The use of Fe(OAc)2 or Mn(OAc)2 (1 equiv) instead of Cu(OAc)2 did not afford any product. The replacement of Cu(OAc)2 with Cu(OTf)2 (1 equiv) only gave 3 a in 30 % yield.
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During the preparation of this manuscript, the rhodium(III)-catalyzed cyclization of aryl nitrones with diaryl alkynes was reported to afford indolines in the absence of copper salts.
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During the preparation of this manuscript, the rhodium(III)-catalyzed cyclization of aryl nitrones with diaryl alkynes was reported to afford indolines in the absence of copper salts:, R. B. Dateer, S. Chang, J. Am. Chem. Soc. 2015, 137, 4908.
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For the formation of by-product 4 a, see the Supporting Information.
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For the formation of by-product 4 a, see the Supporting Information.
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