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2-2,2-bipyridine; Ad-Tripod=1,3,5-tris(p- carboxyphenyl)-7-adamantyl. The Ad-tripod notation is different from that used in our previous publications. In this paper the phenyl group in position 7 is considered part of the bridge.
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4444231617
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note
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The use of an ethynyl bridge carrying the chromophore in Route A is not advantageous because it leads to a mixture, and is not feasible with chromophores that are incompatible with the organolithium reagents used in the carboxylation step.
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49
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0028550334
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This is readily synthesized in multi-gram amounts and in two steps from 1-bromoadamantane: V.R. Eicher, and L.J. Mathias Macromolecules 27 1994 7015
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1-Bis(ethynyl)-bicyclo[2.2.2]octane, with or without trialkylsilyl protecting groups, has been prepared by others, see for instance: Honegger, E.; Heilbronner, E.; Heß, N.; Martin, H. -D. Chem. Ber. 1987, 120, 187 and Ref. 18. We prepared it in two steps from bicyclo[2.2.2]octane-1,4- dicarboxyaldehyde (Kumar, K.; Wang, S. S.; Sukenik, C. N. J. Org. Chem. 1984, 49, 665) following the method reported for the synthesis of 1,4- bis(trimethylsilylethynyl)-cubane and 1,4-bis(ethynyl)-cubane from cubane-1,4-dicarboxyaldehyde (Eaton, P. E.; Galoppini, E.; Gilardi, R. J. Am. Chem. Soc. 1994, 116, 7588).
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4444320549
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Tetrasubstituted products were not observed or found in trace amounts in this step
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-
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60
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0034614856
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63
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4444311243
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note
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1H NMR of the mixture (see Supplementary data), (ii) the observation that 14 does not react in the cross coupling step, (iii) the observation that the polarity on silica is identical to that of 13, similar to what we have experienced when a H is replaced by a I group in tetraphenylmethane derivatives. Unreacted 14 was separated from the product after the cross-coupling, but could never be isolated in pure form
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