Abstract
High-content Dewar benzene polymers and sterically congested [n ]-ladderanes have been synthesized from [4πs +2πs ] cyclobutadienemetal complex cycloaddition chemistry. In the former case, tetramethylcyclobutadiene-AlCl3 is reacted with an acetylene-containing precursor polymer to yield > 95% Dewar benzene
incorporation. In the latter case, [n ]-ladderanes containing up to thirteen rings are prepared via a one-pot procedure
from 2-butyne.
Key words
polymer synthesis - Dewar benzene - [n ]-ladderanes - cycloadditions - cyclobutadiene
References
<A NAME="RC00703ST-1">1 </A> For a comprehensive review of cyclobutadienemetal complexes, see:
Efraty A.
Chem. Rev.
1977,
77:
691
<A NAME="RC00703ST-2">2 </A>
Koster JB.
Timmermans GJ.
van Bekkum H.
Synthesis
1971,
139
<A NAME="RC00703ST-3">3 </A>
Gleiter R.
Treptow B.
J. Org. Chem.
1993,
58:
7740
<A NAME="RC00703ST-4">4 </A>
Gleiter R.
Treptow B.
Angew. Chem., Int. Ed. Engl.
1990,
29:
1427
<A NAME="RC00703ST-5">5 </A>
Gleiter R.
Ohlbach F.
Oeser T.
Irngartinger H.
Liebigs Ann. Chem.
1996,
785
<A NAME="RC00703ST-6">6 </A>
Marsella MJ.
Meyer MM.
Tham FS.
Org. Lett.
2001,
3:
3847
<A NAME="RC00703ST-7">7 </A>
Mehta G.
Viswanath MB.
Kunwar AC.
J. Org. Chem.
1994,
59:
6131
<A NAME="RC00703ST-8">8 </A>
Calculations were performed using Titan computational software, Schrodinger, Inc.,
1500 SW First Avenue, Suite 1180, Portland, Oregon 97201.
<A NAME="RC00703ST-9">9 </A>
Hopf H.
Angew. Chem. Int. Ed.
2003,
42:
2822
<A NAME="RC00703ST-10">10 </A>
Li W.
Fox MA.
J. Am. Chem. Soc.
1996,
118:
11752