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Dppe = 1,2-bis(diphenylphosphino)ethane, dppp = 1,3- bis(diphenylphosphino)propane, dppb = 1,4-bis(diphenylphosphino)butane, dppm = 1,1-bis(diphenylphosphino)methane, dpp-benzene = 1,2-bis(diphenylphosphino) benzene, dcpe = 1,2-bis(dicydohexylphosphino)ethane, BINAP = (±)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, dpe-phos = bis(2-diphenylphosphinophenyl)ether, dppf = 1,1′- bis(diphenylphosphinoferrocene), xantphos = 9,9-dimethyl-4,5- bis(diphenylphosphino)xanthene.
-
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35
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20944447030
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note
-
Our previous studies showed that use of certain electron-rich phosphines (e.g., 2-dicyclohexylphosphinobiphenyl) provided acceptable yields in the Pd-catalyzed carboamination reactions of γ-aminoalkenes. Thus, it seemed possible that the alkene insertion into the Pd-N bond may also potentially proceed with other electron-rich phosphines. See ref 2.
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20944434812
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note
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The rate of C-N bond-forming reductive elimination decreases as the nitrogen becomes less nucleophilic. See: (a) Reference 12b.
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The rate of reductive elimination generally increases as ligand size increases and decreases as ligand basicity increases. Steric effects can outweigh electronic effects, as electron-rich ligands that are sterically bulky are known to promote reductive elimination. For reviews, see: (a) Christmann, U.; Vilar, R. Angew. Chem., Int. Ed. 2005, 44, 366-374.
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8-Pd(II) complexes generally occur via an associative mechanism. See: (a) Shultz, L. H.; Tempel, D. J.; Brookhart, M. J. Am. Chem. Soc. 2001, 123, 11539-11555 and references therein.
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Rates of associative ligand substitution should decrease as the electron density on the metal center increases due to electron-electron repulsion between the metal and the incoming nucleophile.
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50
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Increased back-bonding from the electron-rich metal to the alkene may also play a role in decreasing the rate of alkene dissociation. For a discussion of back-bonding in electron-rich Pd(II)-alkene complexes, see: Miki, K.; Shiotani, O.; Kai, Y.; Kasai, N.; Kanatani, H.; Kurosawa, H. Organometallics 1983, 2, 585-593.
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Use of trimesitylphosphine provided a very complex mixture of unidentified products.
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3 as ligands afforded isolated yields of 54, 44, and 53%, respectively.
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73
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20944444913
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note
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1H NMR). The small differences in the product ratios for these are likely due to experimental error associated with the measurement techniques.
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74
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20944437151
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The mechanism for Pd-catalyzed N-arylation reactions of amines is well-documented and is believed to proceed via intermediate palladium(aryl) (amido) complexes such as 6. For lead references, see: (a) Reference 5.
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4 or dppp at 110 °C in toluene did not result in any detectable reaction.
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88
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0036015597
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Zuideveld, M. A.; Swennenhuis, B. H. G.; Boele, M. D. K.; Guari, Y.; van Strijdonck, G. P. F.; Reek, J. N. H.; Kamer, P. C. J.; Goubitz, K.; Fraanje, J.; Lutz, M.; Spek, A. L.; van Leeuwen, P. W. N. M. J. Chem. Soc., Dalton Trans. 2002, 2308-2317.
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(2002)
J. Chem. Soc., Dalton Trans.
, pp. 2308-2317
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Zuideveld, M.A.1
Swennenhuis, B.H.G.2
Boele, M.D.K.3
Guari, Y.4
Van Strijdonck, G.P.F.5
Reek, J.N.H.6
Kamer, P.C.J.7
Goubitz, K.8
Fraanje, J.9
Lutz, M.10
Spek, A.L.11
Van Leeuwen, P.W.N.M.12
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90
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-
0037138687
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-
and references therein
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Ligand 11 is believed to act as a bidentate ligand via complexation of the aromatic ring bearing the dimethylamino group. See: Yin, J.; Rainka, M. P.; Zhang, X.-X.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 1162-1163 and references therein.
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(2002)
J. Am. Chem. Soc.
, vol.124
, pp. 1162-1163
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Yin, J.1
Rainka, M.P.2
Zhang, X.-X.3
Buchwald, S.L.4
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91
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0001369373
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Ozawa, F.; Kurihara, K.; Fujimori, M.; Hidaka, T.; Toyoshima, T.; Yamamoto, A. Organometallics 1989, 8, 180-188.
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(1989)
Organometallics
, vol.8
, pp. 180-188
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Ozawa, F.1
Kurihara, K.2
Fujimori, M.3
Hidaka, T.4
Toyoshima, T.5
Yamamoto, A.6
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