The first examples of the reactions of Fischer carbene complexes
with 1,3-butadiynes are reported. These
reactions are of interest since they provide new methods for the
synthesis of acetylenic substituted arenes and also
for the synthesis of biaryls. The reactions of the complexes
(CO)5CrC(OR1)R2
[R1 = Me, n-Bu; R2 =
phenyl,
1-naphthyl, 1-cyclohexenyl] were investigated with the conjugated
diynes R3C⋮CC⋮CR3 [R3 =
t-Bu, i-Pr, Ph].
All of the carbene complexes will react with 1 equiv of the diyne
to give good yields of acetylenic arenes 5, 19,
and
23, each with high selectivity for the regioisomer in which
the substituent R3 on the diyne is incorporated
adjacent
to the phenol function. The reactions of the alkynylarenes
5, 19, and 23 with a second equivalent
of carbene complexes,
4, 16, and 22, respectively, generate
the bis-phenols 26, 31, and 33, with
varying amounts of five-membered-ring
annulated compounds as side products. These side products are not
seen with the cyclohexenyl complex 22 and can
be minimized to some extent for the phenyl complex 4a by
proper control of the concentration and the temperature.
Attempts to carry out benzannulations of both of the acetylenic
functions in the 1,3-diyne concurrently by employing
2 equiv of the carbene complex were not successful, and this is
suspected to be due to the presence of a chromium
tricarbonyl group on the newly formed arene ring after the first
benzannulation, such as in complex 34. The
concurrent
double benzannulation of a diyne can be achieved in an intramolecular
fashion with the bis-carbene complex 39.
The intramolecular process leads to a reversal in the
regiochemistry of the second benzannulation producing the
C
2-symmetrical 2,2‘-binaphthol 40
from the reaction of complex 39 with the diyne 8
along with the indenylnaphthalene
41. The reaction of the optically pure bis-carbene
complex 44 derived from
(2R,3R)-butane-2,3-diol with diyne
8
gives a single diastereomer of the 2,2‘-binaphthol 46.
Chemical correlation with the known 2,2‘-binaphthol 51
reveals
that the biaryl axis in 46 has an
S-configuration, which was predicted from an examination of
models.