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For reports on the syntheses of bis-2,2'-bipyridines with short conjugated bridges, and the properties of their dinuclear metal complexes see;
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For a discussion concerning generalized strategies for oligomer synthesis, see for example:
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33847533107
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For early reports on the direct ethynylation of brominated 2,2'bipyridines using the Sonogashira protocol, see:
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41
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(b) Suffert, J.; Ziessel, R. Tetrahedron Lett. 1991,32, 757. This methodology has been extended to the syntheses of linear, terminally unfunctionalized bis-(2,2'bipyridine) ligands bearing ethyne and diethyne bridges via a more convergent approach.
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Grosshenny, V.; Romero, F. M.; Ziessel, R. J. Org. Chem. 1997, 62, 1491. An identical methodology has been communicated to yield terminally unfunctionalized aryldiethynebridged bis(2,2'-bipyridines), but full product characterization and experimental details were not reported,
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33847555203
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note
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It must be emphasized that the poor solubility expected of larger ligand architectures may not necessarily hamper the processibility and usefulness of the resulting metal complexes. In the case of ligand scaffolds coordinated by charge-neutral metal complexes, ancillary metal-bound ligands may act as the solubilizing components. For ionic complexes, the coûterions may endow solubility-enhancing properties to the resulting superstructure.
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46
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85004366048
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2-Chloro-3-iodopyridine and 2,6-dimethyl-3-iodol-chloropyridine are both reported to undergo selective palladium-catalyzed ethynylation at the 3-iodo substituent: Sakamoto, T.; Kondo, Y.; Watanabe, R.; Yamanaka, H. Chem. Pharm. Bull. 1986, 34, 2719.
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47
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For examples of 2,2'-bipyridine syntheses via Stille crosscouplings with 2-chloropyridines, see for example: (a) Ghadiri, M. R.; Soares, C.; Choi, C. J. Am. Chem. Soc. 1992, 114, 825.
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55
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37049081400
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Syntheses of l,3,5-tris(pyridylethynyl)benzenes appear to be rare in the literature. For a preparation of l,3,5-tris(4-pyridylethynyl)benzene, see: Anderson, H. L.; Walter, C. J.; Vidal-Ferran, A.; Hay, R. A.; Lowden, P. A.; Sanders, J. K. M. J. Chem. Soc., Perkin Trans, l 1995, 2275.
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33847542577
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note
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The reaction of 15b with iodobenzene and l-bromo-4-(trimethylsilylethynyDbenzene under Sonogashira conditions provided the respective 2KWoro-5-(ethynylphenyl)pyridineand2-ch!or6-5-(1-th-nyl4- trimethylsilylethynylphenyDpyridine in >70% isolated yields: P. N. W. Baxter, unpublished results.
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33847553620
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note
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If the Sonogashira and Negishi cross-coupling reactions with 13a and 12a, respectively, are performed using 2-bromo-5-iodopyridine in place of 9, then chemoselectivity is lost and product mixtures are obtained, which arise from reaction at both the 2- and 5-pyridine ring positions.
-
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64
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0000131734
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For a detailed investigation into the influence of the catalyst upon the rate, yield, and temperature dependence of the Stille crosscoupling reaction, see: Farina, V.; Krishnan, B. J. Am. Chem. Soc. 1991, 113, 9585.
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33847560531
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note
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Yield reductions have also been observed in the Sonogashiratype synthesis of a phenyl-l,2-bis(meso-ethynylporphyrin) system:
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70
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(a) Arnold, D. P.; Nitschinsk, L. J. Tetrahedron Lett. 1993, 34, 693. For investigations on the thermal rearrangements of phenyl-l,2-ethynes, see:
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33847545486
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The bis- and tris-5-(2-chloropyridines) incorporating ethyne moieties in their bridges will be expected to experience an increased electronic communication between the 2-chloro groups of the terminal pyridine rings in the case of 5a and 5f, and to a lesser extent 6-8. The 2-chloro groups of the 5-(2-chloropyridines) 5f,g, and 6-8 would also be strongly electronically linked to the bridging phenyl and biphenyl rings. Both situations would result in a net electronwithdrawing effect upon the 2-chloro substituents of 5a, 5f,g, and 6-8. It is well documented that the rates and yields of Stille cross-coupling reactions with aryl- and vinyltrialkyltin reagents are enhanced by the presence of electron-withdrawing substituents on the aryl-halide component. See for example: (a) Stille, J. K. Angew. Chem., Int. Ed. Engl. 1986,25, 516
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0346184325
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The lower reactivity of 5b and 5c toward double Stille cross-couplings with 18b may therefore result from a lack of reactivity enhancement of the chlorine groups, due to poorer electronic communication through the phenyl and biphenyl bridges. In this case, catalyst decomposition effectively competes with bis-5-(2,2'-bipyridine) formation.
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(b) McKean, D. R.; Parrinello, G.; Renaldo, A. F.; Stille, J. K. J. Org. Chem. 1987, 52, 422. The lower reactivity of 5b and 5c toward double Stille cross-couplings with 18b may therefore result from a lack of reactivity enhancement of the chlorine groups, due to poorer electronic communication through the phenyl and biphenyl bridges. In this case, catalyst decomposition effectively competes with bis-5-(2,2'-bipyridine) formation.
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For an assignment of the UV absorption spectrum of 2,2'bipyridine, see:
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77
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33847563899
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Vögtle, F., Ed.; B. G. Teubner: Stuttgart, Chapter 2, p and references therein.
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