Preparation and reactivity of [D3d]-octahedrane: the most stable (CH)12 hydrocarbon.
The synthesis of the (CH)12 hydrocarbon [D(3d)]-octahedrane (heptacyclo[6.4.0.0(2,4).0(3,7).0(5,12).0(6,10).0(9,11)]dodecane) 1 and its selective functionalization retaining the hydrocarbon cage is described. The B3LYP/6-311+G* strain energy of 1 is 83.7 kcal mol(-1) (4.7 kcal mol(-1) per C-C bond) which is significantly higher than that of the structurally related (CH)16 [D(4d)]-decahedrane 2 (75.4 kcal mol(-1); 3.1 kcal mol(-1) per C-C bond) and (CH)20 [I(h)]-dodecahedrane 3 (51.5 kcal mol(-1); 1.7 kcal mol(-1) per C-C bond); the heats of formation for 1-3 computed according to homodesmotic equations are 52, 35, and 4 kcal mol(-1). Catalytic hydrogenation of 1 leads to consecutive opening of the two cyclopropane rings to give C2-bisseco-octahedrane (pentacyclo[6.4.0.0(2,6).0(3,11).0(4,9)]dodecane) 16 as the major product. Although 1 is highly strained, its carbon skeleton is kinetically quite stable: Upon heating, 1 does not decompose until above 180 degrees C. The B3LYP/6-31G* barriers for the S(R)2 attack of the tBuO. and Br3C. radicals on a carbon atom of one of the cyclopropane fragments (Delta(298) = 27-28 kcal mol(-1)) are higher than those for hydrogen atom abstraction. The latter barriers are virtually identical for the abstraction from the C1-H and C2-H positions with the tBuO. radical (DeltaG(298) = 17.4 and 17.9 kcal mol(-1), respectively), but significantly different for the reaction at these positions with the Br3C. radical (DeltaG(298) = 18.8 and 21.0 kcal mol(-1)). These computational results agree well with experiments, in which the chlorination of 1 with tert-butyl hypochlorite gave a mixture of 1- and 2-chlorooctahedranes (ratio 3:2). The bromination with carbon tetrabromide under phase-transfer catalytic (PTC) conditions (nBu4NBr/NaOH) selectively gave 1-bromooctahedrane in 43 % isolated yield. For comparison, the PTC bromination was also applied to 2,4-dehydroadamantane yielding 54 % 7-bromo-2,4-dehydroadamantane.
de Meijere
Armin
A
Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Germany. Armin.deMeijere@chemie.uni-goettingen.de
Lee
Chi-Hung
CH
Kuznetsov
Mikhail A
MA
Gusev
Dmitriy V
DV
Kozhushkov
Sergei I
SI
Fokin
Andrey A
AA
Schreiner
Peter R
PR