RING-OPENING OF BICYCLO[N.1.0]ALKANONES TO 2-CYCLOALKANONE-1,3-DIYLS - WHY DOES OXYALLYL DIRADICAL FORMATION REQUIRE LESS ENERGY FROM BICYCLO[3.1.0]HEXAN-6-ONES THAN FROM BICYCLO[1.1.0]BUTAN-2-ONES
Da. Hrovat et al., RING-OPENING OF BICYCLO[N.1.0]ALKANONES TO 2-CYCLOALKANONE-1,3-DIYLS - WHY DOES OXYALLYL DIRADICAL FORMATION REQUIRE LESS ENERGY FROM BICYCLO[3.1.0]HEXAN-6-ONES THAN FROM BICYCLO[1.1.0]BUTAN-2-ONES, Journal of the American Chemical Society, 118(17), 1996, pp. 4159-4166
CASSCF and CASPT2N/6-31G calculations have been performed on the open
ing of bicyclo[n.1.0]-alkanones, n = 1-3 (1-3), to the corresponding 2
-cycloalkanone-1,3-diyls (4-6). In agreement with the failure to obser
ve 1,4-dimethylbicyclo[2.1.0]pentan-5-one (2b) experimentally, ring-op
ened 2-cyclopentanone-1,3-diyl diradicals (5) are calculated to be low
er in energy than the corresponding bicyclo[2.1.0]pentan-5-ones (2). A
lso, in agreement with kinetic experiments on di-tert-butyl derivative
s 1c and 3c, bicyclo[3.1.0]hexan-6-ones (3) are calculated to undergo
ring opening more easily than bicycio[1.1.0]butan-2-ones (1). This res
ult is surprising since bicyclo[1.1.0]butane (7a) is both calculated a
nd found to have a higher strain energy than bicyclo[3.1.0]hexane (9a)
. Isodesmic reactions are used to show that the comparative reluctance
of bicydo[1.1.0]butan-2-ones (1) to undergo ring opening to 2 cyclobu
tanone-1,3-diyls (4) is primarily due to the stabilization of 1 by a s
trong interaction between the bent bond between the bridgehead carbons
, C-1 and C-3, and the carbonyl group at C-2. Ab initio calculations o
f the energies of isodesmic reactions are also used to show that methy
l substituents provide considerable stabilization for oxyallyl diradic
als 4b-6b, and DFT calculations reveal that steric interactions betwee
n the tert-butyl groups in 3c play a minor role in reducing the energy
required for its ring opening to 6c, relative to that required for op
ening of 1c to 4c.