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nM-X") to intermediate A is shown in Scheme 1 as a single step, generating one equivalent of HX. Such a one-step process is often used to describe an electrophilic substitution pathway for C-H bond activation. However, we would like to clarify that the current one-step transformation is a simplified description and does not imply an electrophilic substitution pathway (see the Results and Discussion for details).
-
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15
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77049118780
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note
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b) The proposed intramolecular imine coordination in intermediate B is likely to occur through a p complexation by the C=N moiety. As one of the reviewers kindly pointed out, the alternative coordination mode, s complexation by the nitrogen atom, would limit the rotation of the electrophile (C=N moiety). This would disturb the orbital interaction that is necessary for the proposed intramolecular imine insertion and, as a result, inhibit the formation of the carbocycle. For a related example with intramolecular coordination by the imine nitrogen that led to the heterocycle formation, please see reference [11e].
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It is likely that the low yields resulted from competitive pathways mediated by rhodium hydride species. However, attempted reactions with various added hydrogen acceptors did not give improved yields
-
It is likely that the low yields resulted from competitive pathways mediated by rhodium hydride species. However, attempted reactions with various added hydrogen acceptors did not give improved yields.
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69
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77049108975
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note
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It is likely that terminal alkynes formed unproductive rhodium-alkynyl complexes, although detection of such species was not attempted. The lack of reactivity of trialkylsilyl-substituted alkynes could result from the steric hindrance or electronic effects from the silyl functionality.
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70
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77049119757
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Styrene and n-butyl acrylate were also tested as olefin substrates, but neither showed any reactivity with the current catalyst system
-
Styrene and n-butyl acrylate were also tested as olefin substrates, but neither showed any reactivity with the current catalyst system.
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note
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An alternative and common C-H alkenylation mechanism involves generation of an arylrhodiumACHTUNGTRENUNG(III) hydrido intermediate, followed by alkyne insertion into the RhIII-hydride linkage and subsequent C-C reduction elimination, see references [2a, h] for detailed discussions.
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72
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67449127136
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nM-X" would generate a RhIII intermediate; subsewww quent loss of HX through reductive elimination would generate the proposed arylrhodium(I) intermediate A as shown in Scheme 1 (see ref. [2] for detailed discussions). For a recent mechanism study, see: L. Li, W. W. Brennessel, W. D. Jones, Organometallics 2009, 28, 3492-3500.
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3-induced rate enhancement could result from the higher reactivity of C-H activation with an electron-poor aryl, or from the higher reactivity of intramolecular addition to an electron-poor imine electrophile
-
3-induced rate enhancement could result from the higher reactivity of C-H activation with an electron-poor aryl, or from the higher reactivity of intramolecular addition to an electron-poor imine electrophile.
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Attempted substrates include acetophenone, benzophenone, Nphenyl benzophenone imine, N-tert-butyl benzaldimine, and benzophenone O-pentafluorobenzoyl oxime
-
Attempted substrates include acetophenone, benzophenone, Nphenyl benzophenone imine, N-tert-butyl benzaldimine, and benzophenone O-pentafluorobenzoyl oxime.
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b) see reference [8] for a comparison of the reactivity of N-unsubstituted ketimines and N-silyl analogues
-
b) see reference [8] for a comparison of the reactivity of N-unsubstituted ketimines and N-silyl analogues.
-
-
-
-
83
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-
0031437633
-
-
III precursors argued against this possibility (Table 1, entries 17-19). For a toluene sulfonic acid (TsOH)-catalyzed cyclization of ortho-alkenyl aromatic ketones, see: P. W. R. Harris, P. D. Woodgate, Synth. Commun. 1997, 27, 4195.
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Synth. Commun.
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Harris, P.W.R.1
Woodgate, P.D.2
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84
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22944460193
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a) M. B. Ezhova, B. O. Patrick, B. R. James, Organometallics 2005, 24, 3753-3757;
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Organometallics
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, pp. 3753-3757
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Ezhova, M.B.1
Patrick, B.O.2
James, B.R.3
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85
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33745840834
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b) M. L. Buil, M. A. Esteruelas, E. Goni, M. Olivan, E. Onate, Organometallics 2006, 25, 3076-3083
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(2006)
Organometallics
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Buil, M.L.1
Esteruelas, M.A.2
Goni, E.3
Olivan, M.4
Onate, E.5
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86
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0033591902
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c) for an example of an aromatic ketone-rhodium(I) complex, see: C. P. Lenges, M. Brookhart, J. Am. Chem. Soc. 1999, 121, 6616-6623.
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J. Am. Chem. Soc.
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Lenges, C.P.1
Brookhart, M.2
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87
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77049127125
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This preparation proceeded with high chemical yields (<80%); the low yield of the isolated product reflected the solubility issue during crystallization
-
This preparation proceeded with high chemical yields (<80%); the low yield of the isolated product reflected the solubility issue during crystallization.
-
-
-
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88
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-
77049123974
-
-
See the Supporting Information for details
-
See the Supporting Information for details.
-
-
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89
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0000532947
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-
a) M. A. Esteruelas, F. J. Lahoz, M. Olivan, E. Onate, L. A. Oro, Organometallics 1994, 13, 3315-3323
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(1994)
Organometallics
, vol.13
, pp. 3315-3323
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Esteruelas, M.A.1
Lahoz, F.J.2
Olivan, M.3
Onate, E.4
Oro, L.A.5
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91
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33748554177
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c) W. J. Marshall, G. Aullon, S. Alvarez, K. D. Dobbs, V. V. Grushin, Eur. J. Inorg. Chem. 2006, 3340-3345.
-
(2006)
Eur. J. Inorg. Chem.
, pp. 3340-3345
-
-
Marshall, W.J.1
Aullon, G.2
Alvarez, S.3
Dobbs, K.D.4
Grushin, V.V.5
-
92
-
-
77049122587
-
-
GC analysis was carried out after the reaction was quenched with dry MeOH. The major product was the recovered benzophenone imine 1a.
-
GC analysis was carried out after the reaction was quenched with dry MeOH. The major product was the recovered benzophenone imine 1a.
-
-
-
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93
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0008894438
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SHELXTL, version 5.1, Bruker-AXS, Madison, WI
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G. M. Sheldrick, Crystallographic Software Package, SHELXTL, version 5.1, Bruker-AXS, Madison, WI, 1998.
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(1998)
Crystallographic Software Package
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Sheldrick, G.M.1
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