49700-70-1Relevant academic research and scientific papers
182. The Aluminum-Bromide-Catalyzed Adamantane Rearrangemet of syn- and anti-Tricyclo2,5>decane
Brossi, Marco,Ganter, Camille
, p. 1963 - 1966 (1987)
In the presence of AlBr3 in CS2 at temperatures below 0 deg C, syn-tricyclo2,5>decane (1) isomerizes exclusively to anti-tricyclo2,5>decane (2) at a higher rate than the latter rearranges to 2-exo,3-exo-trimethylene-8,9,10-trinorbornane (4).However, at temperatures above 0 deg C, the anti isomer 2 isomerizes to 4 faster than 1 to 2 and 4.As a consequence, hydride abstraction occurs at C(3) (->carbocation a, which rearranges to carbocation b (anti skeleton)) in the syn-isomer 1 and more readily at C(9) (->carbocation c) than at C(3) (->carbocation b) in the anti-isomer 2.
The Adamantane Rearrangement of syn- and anti-Tricyclo2,5>decane. Part II. Rearrangements Initiated by Regioselective Formation of Carbocations at C(3) and C(9)
Brossi, Marco,Ganter, Camille
, p. 848 - 858 (2007/10/02)
The endo- and exo-alcohols 5-12 of syn- (1) and anti-tricyclo2,5>decane (2) were treated with BF3/Et3SiH (ionic hydrogenation) in order to study the behaviour of the corresponding regioselectively generated carbocations at C(3) (a (syn), b (anti) and C(9) (c (syn), d (anti)).The anti-hydrocarbon 2 is practically the sole product obtained starting with the four 3-alcohols (via a -> b from 5 and 6 (syn) and via b from 9 and 10 (anti)).The four 9-alcohols in each case yield a mixture of 2-endo,3-endo- (3) and 2-exo,3-exo-trimethylene-8,9,10-trinorbornane (4) (via c -> e from 7 and 8 (syn) and via d -> f from 11 and 12 (anti)), but no hydrocarbon 2, i.e. none of the 1,3-H shifts c -> a and d -> b is involved.
