Diynes future

The total synthesis of ( )-estrone [( )-1 ] by Vollhardt et al. is a novel extension of transition metal mediated alkyne cyclotrimeriza-tion technology. This remarkable total synthesis is achieved in only five steps from 2-methylcyclopentenone (19) in an overall yield of 22%. The most striking maneuver in this synthesis is, of course, the construction of tetracycle 13 from the comparatively simple diyne 16 by combining cobalt-mediated and ort/io-quinodimethane cycloaddition reactions. This achievement bodes well for future applications of this chemistry to the total synthesis of other natural products. 

Although the bulk of PDA sensors involve vesicles and Langmuir monolayers, a few examples of responsive PDA assemblies based on bolaamphiphiles and diyne silica nanocomposites have been reported (Lu et al. 2001 Song et al. 2001, 2004 Yang et al. 2003 Peng et al. 2006). Although these materials have not been broadly utilized for analyte sensing, they do exhibit the thermochromic, solvatochro-mic, and pH responsive behavior seen with monolayers and liposomes and hold promise for future development. 

Scheme 3.55 shows the synthesis of the quinone-containing molecular system with alligator clips on both ends (5). This compound can be used to crosslink metallic nanoparticles for bridging connections in future molecular electronic devices. 11 was cross-coupled with an excess of TMSA followed by a subsequent deprotection to cleanly afforded the diyne 18. This was... 

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