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While 6-substituted 2-pyridylphosphanes are usually synthesized by phosphination of the 2-halo precursors (see ref. [4a]). there is no single obvious synthetic route for the latter. For example, a recent paper on catalysis described syntheses of four 6-substituted 2-diphenylphosphinopyridines, in which each of the halogenated precursors was obtained by a different approach: L. P. Spencer, R. Altwer, P. Wei, L. Gelmini, J. Gauld, D. W Stephan, Organometallics 2003, 22, 3841.
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While 6-substituted 2-pyridylphosphanes are usually synthesized by phosphination of the 2-halo precursors (see ref. [4a]). there is no single obvious synthetic route for the latter. For example, a recent paper on catalysis described syntheses of four 6-substituted 2-diphenylphosphinopyridines, in which each of the halogenated precursors was obtained by a different approach: L. P. Spencer, R. Altwer, P. Wei, L. Gelmini, J. Gauld, D. W Stephan, Organometallics 2003, 22, 3841.
-
-
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-
35
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-
67650614731
-
-
Based on the synthetic methods reported here, the compounds L8 (ALPYPHOS) and L15 (ARPYPHOS) have been prepared on a large scale and are currently on offer from the Aldrich chemical company.
-
Based on the synthetic methods reported here, the compounds L8 ("ALPYPHOS") and L15 ("ARPYPHOS") have been prepared on a large scale and are currently on offer from the Aldrich chemical company.
-
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36
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0001629532
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Catalytic amounts of CuI were added, which may not be necessary. For copper-mediated phosphinations, see
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For this comparison, several X-ray crystal structures from the CSD database have been considered: ALATUC, PODWUA, WILJOQ, and WILPIQ
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For this comparison, several X-ray crystal structures from the CSD database have been considered: ALATUC, PODWUA, WILJOQ, and WILPIQ.
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67
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67650638353
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Diego State University, has informed us that this synthesis has been optimized in his group to give higher overall, yields. Nevertheless, the lengthy route and overall yield are still unsatisfactory. Personal communication by e-mail, 2006
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Prof. D. B. Grotjahn, San. Diego State University, has informed us that this synthesis has been optimized in his group to give higher overall, yields. Nevertheless, the lengthy route and overall yield are still unsatisfactory. Personal communication by e-mail, 2006.
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Prof1
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San3
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68
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67650594296
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3 in hot acetonitrile; see the Supporting Information.
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3 in hot acetonitrile; see the Supporting Information.
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70
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13644268558
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67650607523
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For monosubstitutions with aryl metals, see: a
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37349117351
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IPr-HCl.=N,N'-bis(2,6-diisopropylphenyl)imidazolium chloride; this material was prepared according to our improved procedure: L. Hintermann, Beilstein J. Org. Chem. 2007, 3, 22.
-
IPr-HCl.=N,N'-bis(2,6-diisopropylphenyl)imidazolium chloride; this material was prepared according to our improved procedure: L. Hintermann, Beilstein J. Org. Chem. 2007, 3, 22.
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88
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89
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67650601457
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Incidentally, this appears to be the first reported case of a catalytic cross-coupling reaction of the 2,4,6-triphenylphenyl group
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Incidentally, this appears to be the first reported case of a catalytic cross-coupling reaction of the 2,4,6-triphenylphenyl group.
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90
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0037182002
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For use of thiophenol as a dummy group to desymmetrize 2, 6-dibromopyridine, see: V. Bonnet, F. Mongin, F. Trécourt, G. Quéguiner, P Knochel, Tetrahedron 2002, 58, 4429.
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For use of thiophenol as a "dummy" group to desymmetrize 2, 6-dibromopyridine, see: V. Bonnet, F. Mongin, F. Trécourt, G. Quéguiner, P Knochel, Tetrahedron 2002, 58, 4429.
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The direct conversion, of alkoxypyridines to halopyridines is fairly well documented for methoxy and a few other alkoxy groups: a) M. Shiao, K. Tarng, Heterocycles 1990, 31, 637.
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Due to experimental errors, deviations of ±10% in RCA are not necessarily significant. However, the slightly higher activity induced by L8 over L7 has been reproduced in several independent experiments.
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Due to experimental errors, deviations of ±10% in RCA are not necessarily significant. However, the slightly higher activity induced by L8 over L7 has been reproduced in several independent experiments.
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103
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67650617009
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n values of pyridine (5.2), pyrimidine (1.3), and 1,3,5-triazine (<0): A. Albert, J. N. Phillips, J. Chem, Soc. 1956, 1294.
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n values of pyridine (5.2), pyrimidine (1.3), and 1,3,5-triazine (<0): A. Albert, J. N. Phillips, J. Chem, Soc. 1956, 1294.
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105
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