Methylated Dihydropentafulvalenes and Pentafulvalenides from Tetramethylcyclopentadiene Derivatives

Abstract

Treatment of tetramethylcyclopentadienyllithium (1Li) with CuCl₂ or bromotetramethylcyclopentadiene (4), respectively, as well as reaction of stannylated tetramethylcyclopentadiene with 4 in presence of PdBr₂ gave two isomeric octamethyldihydropentafulvalenes (3 and 5), of which 5 was deprotonated to a highly substituted cyclopentadienyl anion. Conversion of 1Li to iodotetramethylcyclopentadiene (7) and reaction of 7 with cyclopentadienyl anion yielded three tautomers of tetramethyldihydropentafulvalene (8a, 8b,and 8c) or exclusively 8a depending on the conditions. The crystal structures of 3 and 8a have been determined, and the isomers of 8 have been converted into the corresponding dianion.

dihydropentafulvalenes - bicyclopentadiendiyl dianion - coupling - cyclopentadienes - lithiation

References

<A NAME="RT00101SS-1A">1a</A> DeMore WB. Prichard HO. Davidson M. J. Am. Chem. Soc.  1959,  81:  5874 

<A NAME="RT00101SS-1B">1b</A> v. Doering WE. In Theoretical Organic Chemistry. The Kekulé Symposium   Butterworth; London: 1959.  35.

<A NAME="RT00101SS-2">2</A> Toyota A. Koseki S. J. Phys. Chem. A  1998,  102:  6675 

<A NAME="RT00101SS-3A">3a</A> Hong SY. Lee KW. Chem. Mater.  2000,  12:  155 

<A NAME="RT00101SS-3B">3b</A> Hong SY. Chem. Mater.  2000,  12:  495 

<A NAME="RT00101SS-4">4</A> Kolehmainen E. Koivisto J. Nissinen M. Rissanen K. Laihia K. New J. Chem.  1999,  23:  691 

<A NAME="RT00101SS-5">5</A> Youngs WJ. Djebli A. Tessier CA. Organometallics  1991,  10:  2089 

<A NAME="RT00101SS-6A">6a</A> Boese R. Cammack JR. Metzger AJ. Pflug K. Tolman WB. Vollhardt KPC. Weidmann TW. J. Am. Chem. Soc.  1997,  119:  6757 

<A NAME="RT00101SS-6B">6b</A> Astruc D. Electron Transfer and Radical Processes in Transition Metal Chemistry   VCH Publishers; New York: 1995. 

<A NAME="RT00101SS-7A">7a</A> Smart JC. Curtis CJ. Inorg. Chem.  1977,  16:  1788 

<A NAME="RT00101SS-7B">7b</A> Vollhardt KPC. Weidmann TW. Organometallics  1984,  3:  82 

<A NAME="RT00101SS-8">8</A> Escher A. Rutsch W. Neuenschwander M. Helv. Chim. Acta  1986,  69:  1644 

<A NAME="RT00101SS-9A">9a</A> Brand R. Krimmer HP. Lindner HJ. Sturm V. Hafner K. Tetrahedron Lett.  1982,  23:  5131 

<A NAME="RT00101SS-9B">9b</A> Tilset M. Vollhardt KPC. Boese R. Organometallics  1993,  12:  3094 

<A NAME="RT00101SS-9C">9c</A> Hirao T. Kurashina M. Aramaki K. Nishihara H. J. Chem. Soc., Dalton Trans.  1996,  2929 

<A NAME="RT00101SS-9D">9d</A> Nicolet P. Sanchez JY. Benaboura A. Abadie MJM. Synthesis  1987,  202 

<A NAME="RT00101SS-9E">9e</A> Okuda J. Herdtweck E. Zeller EM. Chem. Ber.  1991,  124:  1575 

<A NAME="RT00101SS-10">10</A> Stille JK. Angew. Chem., Int. Ed. Engl.  1986,  25:  508 

<A NAME="RT00101SS-11A">11a</A> Fritz HP. Kreiter C. J. Organomet. Chem.  1964,  1:  323 

<A NAME="RT00101SS-11B">11b</A> Grishin YK. Sergeyev NM. Ustynyuk YA. J. Organomet. Chem.  1970,  22:  361 

<A NAME="RT00101SS-11C">11c</A> Tupciausas AP. Sergeyev NM. Ustynyuk YA. Org. Magn. Reson.  1971,  3:  655 

<A NAME="RT00101SS-11D">11d</A> Kisin AV. Kerenevski VA. Sergeyev NM. Ustynyuk Y. J. Organomet. Chem.  1972,  34:  93 

<A NAME="RT00101SS-11E">11e</A> Abel EW. Dunster MO. Waters A. J. Organomet. Chem.  1973,  49:  287 

<A NAME="RT00101SS-11F">11f</A> Blümel J. Köhler FH. J. Organomet. Chem.  1988,  340:  303 

<A NAME="RT00101SS-12">12</A> Bildstein B. Hradsky A. Kopacka H. Malleier R. Ongania KH. J. Organomet. Chem.  1997,  540:  127 

<A NAME="RT00101SS-13">13</A> Kaupp G. Boy J. Angew. Chem., Int. Ed. Engl.  1997,  36:  48 

<A NAME="RT00101SS-14A">14a</A> Davies GA. Lusztyk J. J. Chem. Soc., Perkin Trans 2  1981,  692 

<A NAME="RT00101SS-14B">14b</A> Culshaw NP. Walton JC. Hughes L. Ingold KU. J. Chem. Soc., Perkin Trans 2  1993,  879 

<A NAME="RT00101SS-14C">14c</A> Roth WR. Hunold F. Liebigs Ann.  1995,  1119 

<A NAME="RT00101SS-15">15</A> Jutzi P. Schwartzen KH. Mix A. Chem. Ber.  1990,  123:  837 

<A NAME="RT00101SS-16">16</A> Breslow R. Canary JW. J. Am. Chem. Soc.  1991,  113:  3950 

<A NAME="RT00101SS-17">17</A> Hilbig H. Köhler FH. Z. Naturforsch., B  2000,  55:  1099 

<A NAME="RT00101SS-18">18</A> Kalinowski HO. Berger S. Braun S. 13C-NMR-Spektroskopie   Georg Thieme Verlag; Stuttgart: 1984.  74.

<A NAME="RT00101SS-19">19</A> Kohl FX. Kanne D. Jutzi P. Organomet. Chem. Synth.  1986,  3:  381 

<A NAME="RT00101SS-20A">20a</A> Feitler D. Whitesides GM. Inorg. Chem.  1976,  15:  466 

<A NAME="RT00101SS-20B">20b</A> Schmitt G. Özman S. Chem. Ztg.  1976,  100:  143 

<A NAME="RT00101SS-21">21</A> Köhler FH. Doll KH. Z. Naturforsch., B  1982,  37:  144 

<A NAME="RT00101SS-22">22</A>

Further data may be obtained on request from The Director, Cambridge Crystallographic Data Centre, Lensfield Road, Cambridge CB2 1EW, UK by quoting the number CCDC 149911.

<A NAME="RT00101SS-23">23</A>

Fachinformationszentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen, Germany by quoting the number CSD 405749.