Classic inves
tiga
tions of
thermal equilibra
tions be
tween 4,4-
d2- and 6,6-
d2-bicyclo[3.1.0]hex-2-enes (Doering, W. von E.; Ro
th, W. R.
Angew. Chem., Int. Ed. Engl. 1963,
2, 115-122) and among deu
terium-labeled and non-racemic 2-me
thyl-5-isopropylbicyclo[3.1.0]hex-2-enes (
![](/images/gifchars/Del<font color=)
ta.gif" BORDER=0 >
3-
thujenes) (Doering, W. von E.; Lamber
t, J. B.
Tetrahedron 1963,
19, 1989-1994 and Doering, W. von E.; Schmid
t, E. K. G.
Tetrahedron 1971,
27, 2005-2030) and bicyclo[3.1.0]hex-2-enes (Cooke, R. S.; Andrews, U. H.
J. Am. Chem. Soc. 1974,
96, 2974-2980) iden
tified
three differen
t pa
ths leading
to dis
tinc
t degenera
te produc
ts. The equilibra
tions
take place
through [1,3]-carbon shif
ts wi
th
retention,suprafacial and
inversion,antarafacial s
tereochemis
try and a
two-cen
tered epimeriza
tion resul
ting in enan
tiomeriza
tion of
the bicyclic skele
ton
through a "ring-flip" process. Ac
tiva
tion parame
ters for
the ra
te cons
tan
ts
kr,
kf, and
ki associa
ted wi
th
these pa
ths have now been secured:
Ea 43.8, 44.3, 44.8 kcal/mol and log
A 14.1, 14.2, 14.1, respec
tively, nearly iden
tical values, differing by less
than probable error limi
ts, consis
ten
t wi
th a ra
te-de
termining forma
tion followed by a rapid par
ti
tioning of a common diradical in
termedia
te under dynamic con
trol.