Abstract
The solution-phase synthesis of corannulene has been modified and it is now possible
to prepare multi gram quantities of corannulene more efficiently, with considerably
less toxic reagents. Cross-coupling of bromocorannulene with TMS-acetylene and phenylacetylene
affords novel ethynyl-containing corannulene derivatives. Deprotection of TMS-ethynyl
corannulene affords the naked alkyne, which can be cross-coupled with pentafluoroiodobenzene
and bromocorannulene to afford the appropriate alkyne derivatives. The photophysical
properties of this new and novel family of alkyne-containing corannulene derivatives
has been evaluated and all of the new derivatives exhibit low to moderate quantum
efficiencies.
Key words
fullerene - corannulene - alkynes - PAH - cross-coupling
References <A NAME="RC00903ST-1">1 </A>
Department of Chemistry, University of Oregon, Eugene, OR 97403-1253.
<A NAME="RC00903ST-2">2 </A>
For correspondence use Zürich address.
3a </A>
Siegel JS.
Seiders TJ.
Chem. Br.
1995,
313
3b </A>
Rabideau PW.
Sygula A. In Advances in Theoretically Interesting Molecules
Vol. 3:
Thummel RP.
Jai Press Inc.;
Conneticut:
1995.
p.1-36
3c </A>
Rabideau PW.
Sygula A.
Acc. Chem. Res.
1996,
29:
235
3d </A>
Scott LT.
Pure Appl. Chem.
1996,
68:
291
<A NAME="RC00903ST-4">4 </A>
Barth WE.
Lawton RG.
J. Am. Chem. Soc.
1966,
88:
380
5a </A>
Sieders TJ.
Elliott EL.
Grube G.
Siegel JS.
J. Am. Chem. Soc.
1999,
121:
7804
5b </A>
Scott LT.
Pure Appl. Chem.
1996,
68:
291
5c </A>
Cheng P.-C.
PhD Dissertation
University;
Boston:
1996.
p.212
6a </A>
Grube GH.
Elliott EL.
Steffens RJ.
Jones CS.
Baldridge KK.
Siegel JS.
Org. Lett.
2003,
5:
713
6b </A>
Metal-Catalyzed Cross-Coupling Reactions
Diederich FN.
Stang PJ.
Wiley-VCH;
:
.
6c </A>
Tsuji J.
Palladium Reagents and Catalysts, Innovations in Organic Synthesis
Wiley;
New York:
1995.
7a </A>
Eberhard MR.
Wang Z.
Jensen CM.
Chem. Commun.
2002,
818
7b </A>
Morales-Morales D.
Grause C.
Kasaok K.
Redon R.
Cramer RE.
Jensen CM.
Inorg. Chim. Acta.
2000,
300-302:
958
8a </A>
Sonagashira K.
Toda Y.
Hagihara N.
Tetrahedron Lett.
1975,
4467
8b </A> For a recent highlight see:
Tykwinski RR.
Angew. Chem. Int. Ed.
2003,
42:
1566
9a </A>
Anastasia L.
Negishi E.
Org. Lett.
2001,
3:
3111
9b </A>
Yang C.
Nolan SP.
Organometallics
2002,
21:
1020
9c </A>
Plenio H.
Hermann J.
Sehring A.
Chem.-Eur. J.
2000,
6:
1820
9d </A>
Alami M.
Crousse B.
Ferri FJ.
Organomet. Chem.
2001,
624:
114
9e </A>
Batey RA.
Shen M.
Lough A.
J. Org. Lett.
2002,
4:
1411
10a </A>
Scott LT.
Hashemi MM.
Meyer DT.
Warren HB.
J. Am. Chem. Soc.
1991,
113:
7082
10b </A>
Scott LT.
Hashemi MM.
Bratcher MS.
J. Am. Chem. Soc.
1992,
114:
1920
10c </A>
Scott LT.
Cheng P.-C.
Hashemi MM.
Bratcher MS.
Meyer DT.
Warren HB.
J. Am. Chem. Soc.
1997,
119:
10963
<A NAME="RC00903ST-11">11 </A>
Sygula A.
Rabideau PW.
J. Am. Chem. Soc.
1999,
121:
7800
12a </A>
Williams JK.
Cockcroft JK.
Fitch AN.
Angew. Chem., Int. Ed. Engl.
1992,
104:
1666
12b </A>
Williams JK.
Cockcroft JK.
Fitch AN.
Angew. Chem., Int. Ed. Engl.
1992,
31:
1655
12c </A>
Cozzi F.
Siegel JS.
Pure Appl. Chem.
1995,
67:
683
12d </A>
Ponzini F.
Zagha R.
Hardcastle K.
Siegel JS.
Angew. Chem. Int. Ed.
2000,
39:
2323
12e </A>
Nishinaga T.
Nodera N.
Miyata Y.
Komatsu K.
J. Org. Chem.
2002,
67:
6091
13a </A>
Coates GW.
Dunn AR.
Henling LM.
Dougherty DA.
Grubbs RH.
Angew. Chem., Int. Ed. Engl.
1997,
36:
248
13b </A>
Coates GW.
Dunn AR.
Henling LM.
Ziller JW.
Lobkovsky EB.
Grubbs RH.
J. Am. Chem. Soc.
1998,
120:
3641
13c </A>
Weck M.
Dunn AR.
Matsumoto K.
Coates GW.
Lobkovsky EB.
Grubbs RH.
Angew. Chem. Int. Ed.
1999,
38:
2741
14a </A>
Steed JM.
Dixon TA.
Klemperer W.
J. Chem. Phys.
1979,
70:
4940
14b </A>
Claessens M.
Palombini L.
Stein M.-L.
Reisse J.
New. J. Chem.
1982,
6:
595
14c </A>
Almlöf J.
Faegri K.
J. Chem. Phys.
1983,
79:
2284
14d </A>
Laidig KE.
Chem. Phys. Lett.
1991,
185:
483
<A NAME="RC00903ST-15">15 </A>
Desiraju GR.
Angew. Chem., Int. Ed. Engl.
1995,
34:
2311
16a </A>
Verdieck JF.
Jankowski WA.
Mol. Lumin. Int. Conf.
1969,
829
16b </A>
Argentine SM.
Francis AH.
Chen C.-C.
Lieber CM.
Siegel JS.
J. Phys. Chem.
1994,
98:
7350
<A NAME="RC00903ST-17">17 </A>
Rabideau PW.
Abdourazak AH.
Sygula R.
Warner IM.
J. Fluoresc.
1997,
7:
231
<A NAME="RC00903ST-18">18 </A>
Demas JN.
Crosby GA.
J. Phys Chem.
1971,
75:
991
19a </A>
Hamai S.
Hirayama F.
J. Phys. Chem.
1983,
87:
83
19b </A>
Meech SR.
Phillips D.
J. Photochem.
1983,
23:
193
<A NAME="RC00903ST-20">20 </A>
Borchardt A.
Hardcastle K.
Gantzel P.
Siegel JS.
Tetrahedron Lett.
1993,
34:
273
