Generation and reactions of Pentacyclo[4.3.0.0(2,4).0(3,8).0(5,7)]non-4-ene.
The highly pyramidalized alkene, pentacyclo[4.3.0.0(2,4).0(3,8).0(5,7)]non-4-ene (9), has been generated via treatment of 4,5-diiodopentacyclo[4.3.0.0(2,4).0(3,8).0(5,7)]nonane (12) with n-butyllithium and tert-butyllithium. The title alkene has also been trapped as its Diels-Alder adduct with 1,3-diphenylisobenzofuran, 2,5-dimethylfuran, and spiro[2.4]hepta-4,6-diene. Products resulting from alkyllithium addition to the pyramidalized double bond of 9 have been isolated and fully characterized spectroscopically. The geometry, olefin strain energy, heat of hydrogenation, and relative HOMO/LUMO energies of 9 have been obtained by ab initio calculations at the MP2 and B3LYP levels using the 6-31G* basis set.
Forman
Mark A
MA
Department of Chemistry, Saint Joseph's University, 5600 City Avenue, Philadelphia, Pennsylvania 19131.
Moran
Caitlin
C
Herres
Joseph P
JP
Stairs
Jason
J
Chopko
Emily
E
Pozzessere
Anthony
A
Kerrigan
Michael
M
Kelly
Carisa
C
Lowchyj
Lisa
L
Salandria
Kerry
K
Gallo
Annemarie
A
Loutzenhiser
Elizabeth
E
D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D007536:Isomerism; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D013816:Thermodynamics
D000475:Alkenes; D006571:Heterocyclic Compounds; D009942:Organometallic Compounds; C046771:butyllithium