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For selected examples, see: a
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For selected examples, see: a) C. Nieto-Oberhuber, M. P. Munoz, E. Bunuel, C. Nevado, D. J. Cardenas, A. M. Echavarren, Angew. Chem. 2004, 116, 2456;
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5156; for a review, see
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33749158251
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1H NMR spectrum of the mixture, as well as the signal at δ = 4.14 ppm expected for the benzylic hydrogen atoms.
-
1H NMR spectrum of the mixture, as well as the signal at δ = 4.14 ppm expected for the benzylic hydrogen atoms.
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31
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31544464934
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For examples of the migration of alkyl groups to Pt carbenoids, see: a H. Kusama, Y. Miyashita, J. Takaya, N. Iwasawa, Org. Lett. 2006, 8, 289;
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For examples of the migration of alkyl groups to Pt carbenoids, see: a) H. Kusama, Y. Miyashita, J. Takaya, N. Iwasawa, Org. Lett. 2006, 8, 289;
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b) J. Sun, M. P. Conley, L. Zhang, S. A. Kozmin, J. Am. Chem. Soc. 2006, 128, 9705;
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c) H. Funami, H. Kusama, N. Iwasawa, Angew. Chem. 2007, 119, 927;
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For selected examples of the Au/Pt-catalyzed preparation of indoles, see: a A. Arcadi, G. Bianchi, F. Marinelli, Synthesis 2004, 610;
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For selected examples of the Au/Pt-catalyzed preparation of indoles, see: a) A. Arcadi, G. Bianchi, F. Marinelli, Synthesis 2004, 610;
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36
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38049016722
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b) K. Cariou, B. Ronan, S. Mignani, L. Fensterbank, M. Malacria, Angew. Chem. 2007, 119, 1913;
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This structural assignment is supported by the isolation and characterization of the side product from the reaction of lactam 7a, in which a methyl group is at the alkyne terminus
-
This structural assignment is supported by the isolation and characterization of the side product from the reaction of lactam 7a, in which a methyl group is at the alkyne terminus.
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39
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38049036133
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III complex as a precatalyst, see: A. S. K. Hashmi, J. P. Weyrauch, M. Rudolph, E. Kurpejovic, Angew. Chem. 2004, 116, 6707;
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III complex as a precatalyst, see: A. S. K. Hashmi, J. P. Weyrauch, M. Rudolph, E. Kurpejovic, Angew. Chem. 2004, 116, 6707;
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33745700263
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for other reactions catalyzed by this complex, see: a
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for other reactions catalyzed by this complex, see: a) S. Wang, L. Zhang, J. Am. Chem. Soc. 2006, 128, 8414;
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A. Fürstner, P. W. Davies, T. Gress, J. Am. Chem. Soc. 2005, 127, 8244.
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Nakamura, I.1
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45
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38049012650
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The reason for this decreased reactivity is not clear, but the molecular sieves may affect the Pt catalyst and partially trap the reactive acylium intermediate
-
The reason for this decreased reactivity is not clear, but the molecular sieves may affect the Pt catalyst and partially trap the reactive acylium intermediate.
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46
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24744464788
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2: B. A. Bhanu Prasad, F. K. Yoshimoto, R. Sarpong, J. Am. Chem. Soc. 2005, 127, 12468.
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2: B. A. Bhanu Prasad, F. K. Yoshimoto, R. Sarpong, J. Am. Chem. Soc. 2005, 127, 12468.
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47
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0000589215
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4, see: a W. Baidossi, M. Lahav, J. Blum, J. Org. Chem. 1997, 62, 669;
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4, see: a) W. Baidossi, M. Lahav, J. Blum, J. Org. Chem. 1997, 62, 669;
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d) J. Marco-Contelles, A. N. Arroyo, S. Anjum, E. Mainetti, N. Marion, K. Cariou, G. Lemière, V. Mouriès, L. Fensterbank, M. Malacria, Eur. J. Org. Chem. 2006, 4618.
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Eur. J. Org. Chem
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51
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The structure of the chloride derivative was assigned on the basis of the close resemblance of the signals in its NMR spectra to those of the bromide product as well as the characteristic isotope pattern in its ESI+ mass spectrum
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+ mass spectrum.
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Additional evidence for the existence of the acylium intermediate C and/or the preceding spiro-zwitterionic intermediate is the formation of the ethyl ester of acid 6 in 30% yield along with the product 4 (45% yield) when EtOH (1.5 equiv) was added to the reaction mixture to trap the intermediates. Moreover, when EtOH (at reflux) was used as the solvent, the ethyl ester was isolated in 68% yield, and the product 4 was observed (< 2%).
-
Additional evidence for the existence of the acylium intermediate C and/or the preceding spiro-zwitterionic intermediate is the formation of the ethyl ester of acid 6 in 30% yield along with the product 4 (45% yield) when EtOH (1.5 equiv) was added to the reaction mixture to trap the intermediates. Moreover, when EtOH (at reflux) was used as the solvent, the ethyl ester was isolated in 68% yield, and the product 4 was observed (< 2%).
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C. A. Witham, P. Mauleon, N. D. Shapiro, B. D. Sherry, F. D. Toste, J. Am. Chem. Soc. 2007, 129, 5838.
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54
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38049006249
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This result also suggests that the evolution of the Pt carbenoid D may not be the rate-limiting step, which would explain why substrates 7 with a primary alkyl group at the alkyne terminus reacted faster than those with an aryl group, although aryl groups usually show greater aptitude for nucleophilic migration
-
This result also suggests that the evolution of the Pt carbenoid D may not be the rate-limiting step, which would explain why substrates 7 with a primary alkyl group at the alkyne terminus reacted faster than those with an aryl group, although aryl groups usually show greater aptitude for nucleophilic migration.
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