A. Burritt et al., CORNER BROMINATION OF 2-METHYL-ENDO-TRICYCLO[3.2.1.0(2,4)]OCTANE AND 2-METHYL-ENDO-TRICYCLO[3.2.1.0(2,4)]OCT-6-ENE, Journal of organic chemistry, 61(11), 1996, pp. 3669-3676
Reaction of 2-methyl-endo-tricyclo[3.2.1.0(2.4)]octane (1) with bromin
e in CCl4 gave 2-exo, 3-endodibromo-2-endo-methylbicyclo[3.2.1]octane
(3) which rearranges on silica to 2-exo, 6-endo-dibromo-1-methylbicycl
o[2.2.2]octane (4). Reaction in methanol gave mo-2-endo-methoxy-2-exo-
methylbicyclo[3.2.1]octane (10) and mo-2-endo-methoxy-2-exo-methylbicy
clo[3.2.1]octane (11) formed by corner attack of the bromine electroph
ile with C2-C4 bond rupture and inversion of configuration at the site
of electrophilic attack. Reaction of 2-methyl-endo-tricyclo[3.2.1.0(2
,4)]oct-6-ene (2) with bromine in CCl4 and methanol gave products of r
eaction at the alkene site.