166
BYKOV et al.
[15] (ëp2ZrHCl) followed by protolysis of the zir-
conocene derivative. We proposed a simple procedure
for the hydrozirconation of triene 3, according to which
ëp2ZrHCl is synthesized in the presence of triene 3 and
hydrozirconation takes place simultaneously with the
formation of ëp2ZrHCl. To increase the selectivity of
the hydrozirconation step, we used a twofold excess of
3. After the reaction, the remaining triene 3 was evapo-
rated in vacuo and the residue containing a nonvolatile
zirconocene derivative was subjected to protolysis by
hydrogen chloride. It is significant from the practical
standpoint that this gives ëp2ZrCl2, which can be iso-
lated and re-used. Hydroboration of diene 4 with
9-BBN affords an intermediate borane which is oxi-
dized to give Z-5-decenol or made to react with
BrCH2COOEt in the presence of ButOK to yield ester 7
with the carbon chain elongated by two atoms
(Scheme 2). Subsequently, ester 7 is reduced by
LiAlH4, giving rise to Z-7-dodecenol, whose acetyla-
tion affords acetate 8.
EXPERIMENTAL
The purity of solvents, initial compounds, and prod-
ucts was checked and the reactions were monitored by
GLC using an LKhM-8MD chromatograph with a
flame ionization detector, an ITs-26 integrating device,
a 50 m × 0.2 mm column, the SKTFP or SE-300 sta-
tionary phase, and ç2 as the carrier gas. H and 13C
1
NMR spectra were recorded on a Bruker MSL-300
spectrometer in ëDël3; the chemical shifts were
referred to TMS. IR spectra were measured on a
Specord IR-75 instrument in thin films. Mass spectra
(EI) were run on a Kratos MS-80 (70 eV). The stereoi-
somer composition was determined on the basis of
GLC and 13C NMR data. All the reactions and the pre-
treatment of initial compounds and solvents were car-
ried out under high-purity argon using LiAlH4 as the
drying agent. Pure compounds were characterized by
mass, 1H and 13C NMR, and IR spectra.
Yet another route of transformations of triene 3 is
related to the hydroboration–iodination protocol. The
reaction of triene 3 with 9-BBN followed by iodination
in the presence of MeONa yields iodinated compound
6, which undergoes cross-coupling with an appropriate
lithium cuprate derivative to give Z-9-tricosene (9) or
2-methyl-Z-7-octadecene (10) (Scheme 2), whose
epoxidation results in Z-7,8-epoxy-2-methyloctade-
cane (11) (Scheme 2). It is worth noting that the cross-
coupling of diiodo derivative 6 with lithium cuprate
reagents gave target products 9 and 10 in low yields.
Therefore, to increase the yield, monoiodinated deriva-
tives were used in the same hydroboration–iodination
and cross-coupling sequence of steps. The same strat-
egy was employed to prepare Z-5-undecenoic acid (12).
First, 1,Z-5-undecadiene was subjected to the hydrobo-
ration–oxidation sequence, giving Z-5-undecenol,
which was then converted into Z-5-undecenoic acid
(12) (Scheme 2); this acid is a component of the phero-
mone of Anghrenus verbasci and, simultaneously, can
serve as an intermediate in the synthesis of heneicos-Z-
6-en-11-one (13) (Scheme 2), which is the sex phero-
mone of the moth Orgiya pseudotsugata.
REFERENCES
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One more application of triene 3 is for the prepara-
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hydroxy acids, precursors of macrocyclic lactones.
Thus, a protocol including successive hydroboration–
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cenoic acid (14), an intermediate en route to Z-5-dode-
cenolide (15) (Scheme 2).
Thus, the first stereoselective cometathesis of COD
and ethylene allowed us to develop a new effective
strategy for the preparation of a number of Z-ene mono-
and bifunctional derivatives which represent practically
valuable biologically active natural products or their
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bret., 1991, no. 28, p. 43.
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