Thermal rearrangements of spiro[2.4]hepta-1,4,6-trienes.
Thermolysis of spiro[2.4]hepta-1,4,6-triene (1a) at 50 degrees C yielded bicyclo[3.2.0]hepta-1,3,6-triene (5), which dimerized in two different fashions to form cyclobutanes. The 1,2-dimethyl and 1-propyl derivatives of 1a also rearranged at 50 degrees C, but at a faster rate, each yielding a pair of cyclobutane dimers. The structures of these symmetrical dimers were investigated by 1D and 2D NMR and NOE difference spectroscopy. Ab initio calculations indicated that the two strained olefins 1a and 5 had comparable energies about 50 kcal/mol lower than norborna-1(7),2,5-triene, which was thus excluded as a reaction intermediate.
Billups
W E
WE
Department of Chemistry, Rice University, Houston, Texas 77005, USA. billups@rice.edu
Saini
Rajesh K
RK
Litosh
Vladislav A
VA
Alemany
Lawrence B
LB
Wilson
William K
WK
Wiberg
Kenneth B
KB