Cyclomagnesation of cycloalkynes with the use of RMgR' catalyzed by zirconium complexes

Article abstract of DOI:10.1134/S1070428009110037

The intermolecular cyclomagnesation of cycloalkynes and joint cyclomagnesation of cycloalkynes and disubstituted acetylenes was carried out by treating with RMgR' (R, R' = Et, Bu, Hlg) in the presence of Cp₂ZrCl₂ as a catalyst. As a

Full text of DOI:10.1134/S1070428009110037

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 11, pp. 1598−1604. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © V.A. D’yakonov, A.A. Makarov, U.M. Dzhemilev, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 11,
pp. 1612−1617.
Cyclomagnesation of Cycloalkynes with the Use of RMgR'
Catalyzed by Zirconium Complexes
V. A. D’yakonov, A. A. Makarov, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, 450075 Russia
e-mail: ink@anrb.ru
Received March 3, 2009
Abstract—The intermolecular cyclomagnesation of cycloalkynes and joint cyclomagnesation of cycloalkynes
and disubstituted acetylenes was carried out by treating with RMgR' (R, R' = Et, Bu, Hlg) in the presence of
Cp2ZrCl2 as a catalyst. As a result new unsaturated bi-and tricyclic organomagnesium compounds were obtained
in high yields.
DOI: 10.1134/S1070428009110037
In the course of the investigation of catalytic cyclo-
magnesation of unsaturated compounds we discovered
for the first time that disubstituted acetylenes reacted
with Grignard reagents in the presence of Cp2ZrCl2
affording tetrasubstituted magnesacyclopenta-2,4-dienes
[1].
BuMgBr, Et2Mg, Bu2Mg) in the presence of zirconium
complexes exhibiting a high activity and selectivity in the
cyclomagnesation of α-olefins [2−4], acetylenes [1],
terminal 1,2-dienes [5, 6], and norbornenes [7].
First the cyclooctyne chosen as model compound was
brought into reaction with BuMgBr (Et2O) under the
conditions developed formerly as optimal for the cyclo-
magnesation of disubstituted acetylenes [1] (~20°C, 2 h,
cyclooctyne−BuMgBr−Cp2ZrCl2, 10 : 20 : 0.5).As a result
of acid hydrolysis and treatment with deuterium oxide of
the reaction products a mixture of four hydrocarbons was
obtained (according to GLC) in an overall yield ~89%.
In continuation of the investigation of this reaction, its
extension to cyclic acetylenes, and also aiming at the
synthesis of new classes of unsaturated fused tricyclic
organomagnesium compounds we studied the reactions
of cycloalkynes (cyclooctyne, cyclododecyne) with
dialkyl and alkylhalogen magnesium derivatives (EtMgBr,
Scheme 1.
[Zr]
n
R
2
2
+
+
+
+
n
n
2
Mg
2
MgR'
2 MgR' R
RMgR'
III, IV
V, VI
I, II
2
VII
H3O+ (D3O+)
R
+
+
+
VII
2
2 X
R
n
n X
X
2
X
XIIà, XIIb, XIIIà, XIIIàb
Xà, Xb, XIà, XIb
VIIIà, VIIIb, IXà, IXb
[Zr] = Cp2ZrCl2; X = H (a), D (b); R = Bu (I, V, VIII, XII), Et (II, VI, IX, XIII); n = 2 (III, X), 6 (IV, XI).
1598

CYCLOMAGNESATION OF CYCLOALKYNES WITH THE USE OF RMgR'
1599
Table 1. Effect of the structure of organomagnesium compound and solvent, and also of the temperature on the yield and
composition of reaction products obtained at treatment of cyclic acetylenes by Grignard reagents catalyzed with Cp2ZrCl2
The structure of organomagnesium compounds I, III,
and V formed in this reaction was established with the
products were identified as 1-butyl-2-deutero-1-
cyclooctene (VIIIb), 2,2'-dideutero-1,1'-bi(1-cyclo-octen-
1-yl) (Xb), 2-butyl-2'-deutero-1,1'-bi(1-cycloocten-1-yl)
(XIIb). 1,4-Dideuterated hydrocarbon Xb formed on the
treatment with deuterium oxide of compound III indicates
that in the latter the Mg atom is linked simultaneously to
atoms C9 and C11. Based on the results obtained we
assumed for compounds I, III, and V the structures of
[2-butyl(1-cycloocten-1-yl)-1-yl]magnesium bromide, 2-
magnesatricyclo[9.6.01,11.03,10]heptadeca-1(11),3(10)-
diene, and [2'-butyl-1,1'-bi(1-cycloocten-1-yl)-2-
yl]magnesium bromide respectively.
1
use of H and 13C NMR spectroscopy, and also by the
mass spectra of the products of their hydrolysis (VIIIa,
Xa, XIIa) and treatment with D2O (VIIIb, Xb, XIIb)
(Scheme 1).
For instance, the 13C NMR spectrum of compound
Xa contained eight signals: two downfield signals at
125.1 and 139.8 ppm assigned to the carbon atoms of the
trisubstituted double bond, and six peaks from sp3-
hybridized carbon atoms of the cyclic fragment in the
region 25–31 ppm testifying to the symmetry of the
molecule. In the 13C NMR spectrum of partially
deuterated compound Xb the signal of the carbon atom
of the double bond is split into a triplet by coupling with
deuterium (JC,D 24.5 Hz) with an α-isotope upfield shift
of the triplet center (Δδ− 0.3 ppm) with respect to the
same signal in the spectrum of compound Xa, and in the
1H NMR spectrum of compound Xb the signal of the
proton at the double bond at 5.77 ppm disappears. The
molecular mass of compounds Xa and Xb equal [M]+
218 and 220 respectively were measured by mass
spectrometry. Similarly was established the structure of
compounds I, V and VII.
In order to increase the chemoselectivity of the
cyclomagnesation,we studied the effect of various factors
(temperature, character of solvent, organomagnesium
compound, ligand surrounding of Zr) on the course of
this reaction (Table 1).
As a result of the above investigations we established
that the reaction of cyclooctyne with BuMgBr in ether
solvents (Et2O, i-Pr2O, THF) without catalyst yielded
products of 1,2-carbomagnesation of the initial acetylene
by BuMgBr I and of intermolecular carbomagnesation
V; the latter might form by the reaction of compound I
with the cyclooctyne. The overall yield of compounds I
and V decreased in the solvent series i-Pr2O > Et2O >
THF in good agreement with the published data on the
growth of the Grignard reagents activity in various solvents
[8]. Based on these results we carried out all further
The above data underlie the assignment to the
hydrolysis products the structures of 1-butyl-1-cyclo-
octene (VIIIa), 1,1'-bi(1-cycloocten-1-yl) (Xa), and 2-butyl-
1,1'-bi(1-cycloocten-1-yl) (XIIa), and the deuterated
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009

D’YAKONOV et al.
1600
Scheme 2.
[Zr] BuMgBr
Br
Br
S8
[Cu]
S
Mg
XIV
III
MeI, [Cu]
Me
XV
Me
XVI
[Zr] = Cp2ZrCl2, [Cu] = CuCl.
Under the developed optimum conditions (BuMgBr,
THF, 20-22°C, 3 h) the yield of magnesacyclopentadiene
III diminished in the series of the tested zirconium-based
catalysts: Cp2ZrCl2 (68%), Ind2ZrCl2 (24%), ZrCl4 (11%),
(BuO)2ZrCl2 (4%), PyZrCl6 (2%).
experiments on cyclomagnesation of cyclic acetylenes
with RMgR' (R, R' = Et, Bu, Hlg) catalyzed by Cp2ZrCl2
in THF solution.
We established that the variation of the temperature
of cyclomagnesation affected both the rate and the
chemoselectivity of the reaction. For instance, at 0°C
within 8 h we obtained magnesacyclopentadiene III in
~56% yield at the selectivity >98%, and at ~40°C in 1 h
a complete conversion of the cyclooctyne was attained,
but under these conditions alongside organomagnesium
compound III formed also carbomagnesation products
I, V, and homocyclotrimer VII.
Cyclododecyne like cyclooctyne under the conditions
we chose entered the reaction of intermolecular
cyclomagnesation with BuMgX (X = Bu, Br) catalyzed
by Cp2ZrCl2 giving 2-magnesatricyclo[13.10.01,15.03,14]-
pentacosa-1(15),3(14)-diene (IV) in 46–56% yield. No
carbomagnesation products formed in these experiments.
To prove reliably the structure of the obtained
magnesacyclopentadiene III and to develop new one-
pot methods of preparation of difficultly available
carbocyclic and heterocyclic compounds we carried out
a series of reactions of compound III with elemental
sulfur, α,α'-dibromo-o-xylene, and methyl iodide [9-11]
and obtained 2-thiatricyclo-[9.6.01,11.03,10]heptadeca-
Replacement of BuMgBr by Bu2Mg, Et2Mg, or
EtMgBr somewhat increased the overall yield of
organomagnesium compounds I−VII and decreased the
chemoselectivity with respect to cyclic compounds III
and IV. Nonetheless, at the use of the above dialkyl and
alkylhalogen magnesium derivatives magnesacyclo-
pentadiene III was obtained in 51−65% yield.
The change in the ratio of the initial reagents by
increasing the content of organomagnesium compound
relative to the cycloalkyne did not result in the increase
in the overall yield of the target organomagnesium
compounds.
1(11),3(10)-diene
(XIV),
3,4-benzotricyclo-
[12.6.01,14.06,13]eicosa-1(14),6(13)-diene (XV), and 2,2'-
dimethyl-1,1'-bi(1-cycloocten-1-yl) (XVI) respectively
(Scheme 2).
The structure of compounds obtained was confirmed
by 1H and 13C NMR spectra and GC-MS method.
Further we attempted a mixed intermolecular
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009

CYCLOMAGNESATION OF CYCLOALKYNES WITH THE USE OF RMgR'
1601
Scheme 3.
R
R
R
n
[Zr]
+
+
BuMgBr
R'
R'
R'
+
Mg
n
n
n
Mg
Mg
R
R'
XIXà_XIXd
XVIIà_XVIId, XVIII
III, IV
R
R
R
H3O+ (D3O+)
+
+
R'
R'
R'
n
n
n
X
X
X
X
X X
XXIVà_XXIVd
XXVà_XXVd
X = H XXà_XXd, XXI
X = D XXIIà_XXIId, XXIII
Xà, Xb
XIà, XIb
[Zr] = Cp2ZrCl2; n = 2 (XVII, XX, XXII); R = R'= Et (a), Pr (b), Bu (c); R = Bu, R'= SiMe3 (d); n = 6, R = R'= Et (XVIII, XXI,
XXIII).
cyclomagnesation of cyclic acetylenes with acyclic
disubstituted acetylenes in order to prepare new class of
bicyclic magnesacyclopenta-2,4-dienes.
6 : 1 : 1. The overall yield reached 86%.
Based on the data of 1D and 2D NMR experiments
and the mass spectra of products from quenching
compound XVIIa with acidified water XXa and deuterium
oxide XXIIa the structure of compound XVIIa was
identified as 10,11-diethyl-9-magnesabicyclo-
[6.2.01,8]undeca-1(8),10(11)-diene.
Actually the reaction of equimolar quantities of cyclo-
octyne and 3-hexyne that we chose as model compounds
with BuMgBr under the conditions developed for homo-
cyclomagnesation of cycloalkynes (BuMgBr, THF, 20-
22°C, 3 h) led to the formation of three types of
magnesacyclopenta-2,4-dienes in a ratio (XVIIa) : (III):
(XIXa) 1 : 5 : 2 (according to the GLC data for hydrolysis
products and products of quenching with D2O) in 77%
yield (Scheme 3). By optimization of the reaction condi-
tions through the variation of the ratio of the initial
compounds (cyclooctyne : 3-hexyne: BuMgBr : Cp2ZrCl2,
10 : 11 : 22:1, 20–22°C, THF, 4 h) we obtained the mixture
of all structural magnesacyclopenta-2,4-dienes XVIIa,
III, and XIXa where the target magnesacyclopenta-
2,4-diene XVIIa was contained in ~64% yield at the ratio
of organomagnesium compounds (XVIIa):(III):(XIXa)
Under the conditions mentioned above the joint cyclo-
magnesation of cyclooctyne with 4-octyne, 5-decyne,
butyltrimethylsilylacetylene, or of cyclododecyne and
3-hexyne in excess BuMgBr led to the formation of the
corresponding bicyclic magnesacyclopenta-2,4-dienes
XVIIb–XVIId, and XVIII in 45–60% yields (Table 2).
The structure of products of joint cyclomagnesation
was reliably proved by spectral methods and by analysis
of quenching the target organomagnesium compounds
with acidified water and deuterium oxide
Thus we for the first time succeeded in intermolecular
Table 2. Joint cyclomagnesation of cyclic and acyclic acetylenes
a Yields of magnesacyles were determined by GLC of the products of their acid hydrolysis.
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D’YAKONOV et al.
1602
homocyclomagnesation of cycloalkynes and mixed cyclo-
magnesation of cycloalkynes with disubstituted acetyl-
enes by treatment with dialkyl magnesium and alkyl-
magnesium halides in the presence of zirconium complexes
resulted in preparation of new types of bi- and tricyclic
magnesa-cyclopenta-2,4-dienes that as shown on several
examples possessed a wide synthetic potential for the
synthesis of carbo-and heterocyclic compounds.
with MgSO4, and subjected to fractional distillation.
1-Butyl-1-cyclooctene (VIIIa), bp 109–111°C
(20 mmHg). 1H NMR spectrum, δ, ppm: 0.91 t (3H,
CH3, J 7 Hz), 1.47 m (12H, CH2), 2.08 m (6H,
CH2CH=C), 5.33 t (1H, CH=C, J 8 Hz). 13C NMR
spectrum, δ, ppm: 14.0 (C12), 22.6 (C11), 26.2 (C6), 26.3
(C5), 26.5 (C4), 28.9 (C7), 29.0 (C3), 30.0 (C10), 30.4
(C9), 37.3 (C8), 123.4 (C2), 141.1 (C1). Found, %: C 86.67;
H 13.33. [M]+ 166. C12H22. Calculated, %: C 86.54;
H 13.30.
EXPERIMENTAL
1-Ethyl-1-cyclooctene (IXa), bp 75–77°C
(20 mm Hg). 1H NMR spectrum, δ, ppm: 0.91 t (3H,
CH3, J 7 Hz), 1.45 m (8H, CH2), 2.11 m (6H,
CH2CH=C), 5.37 t (1H, CH=C, J 8 Hz). 13C NMR
spectrum, δ, ppm: 13.8 (C10), 26.2 (C6), 26.4 (C5), 26.5
(C4), 28.9 (C7), 29.1 (C3), 29.7 (C9), 37.5 (C8), 123.6 (C2),
141.3 (C1). Found, %: C 86.88; H13.12. [M]+ 138. C10H18.
Calculated, %: C 86.73; H 13.10.
Products of hydrolysis and quenching with D2O were
analyzed on a chromatograph Chrom-5 in a flow of helium,
column 1200 × 3 mm, stationary phase 5% SE-30 or 15%
PEG-6000 on Chromaton N-AW. 1H and 13C NMR
spectra were registered on a spectrometer Bruker
Avance-400 (400 and 100 MHz respectively) from
solutions in CDCl3, chemical shifts reported with respect
to TMS. GC-MS measurements were performed on an
instrument Finnigan 4021 (glass capillary column 50000 ×
0.25 mm, stationary phase HP-5, carrier gas helium, ramp
from 50 to 300°C at a rate 5 deg/min, vaporizer tempera-
ture 280°C, ion source temperature 250°C, 70 eV).
Elemental analysis was carried out on an analyzer Karlo
Erba 1106. The yields of organomagnesium compounds
were determined by GLC of hydrolysis products.
Reactions with organometallic compounds were per-
formed in a flow of dry argon. The ether solvents were
distilled over LiAlH4 just before use. Solutions of RMgR'
(R, R' = Bu, Et, Br) in Et2O and THF were prepared by
procedure [12]. Cp2ZrCl2 was synthesized from ZrCl4
as described before [13]. Compounds VII, Xa, Xb, XIa,
XIb, XIV, XVI, XXa–XXc, XXI, XXIIa–XXIIc, XVIII,
XXIVa–XXIVd, XXVa–XXVd were identified by
comparison with authentic samples [1, 14–18].
2-Butyl-1,1'-bi(1-cycloocten-1-yl) (XIIa), bp 154–
1
156°C (1 mm Hg). H NMR spectrum, δ, ppm: 0.94 t
(3H, CH3, J 7 Hz), 1.47 m (20H, CH2), 2.18 m (10H,
CH2C=C), 5.25 t (1H, CH=C, J 8 Hz). 13C NMR
spectrum, δ, ppm: 14.0, 22.5, 26.5 (C4,4'), 26.6 (C5,5'),
26.8, 28.7 (C6,6'), 29.3 (C3'), 29.5 (C7,7'), 29.6 (C3), 29.9
(C8,8'), 31.0, 126.1 (C2'), 135.2 (C1'), 137.9 (C1), 142.1
(C2). Found, %: C 87.51; H 12.49. [M]+ 274. C20H34.
Calculated, %: C 87.44; H 12.45.
2-Ethyl-1,1'-bi(1-cycloocten-1-yl) (XIIIa), bp 136–
1
138°C (1 mm Hg). H NMR spectrum, δ, ppm: 0.95 t
(3H, CH3, J 7 Hz), 1.49 m (16H, CH2), 2.16 m (10H,
CH2C=C), 5.24 t (1H, CH=C, J 8 Hz). 13C NMR
spectrum, δ, ppm: 13.9, 26.4 (C4,4'), 26.6 (C5,5'), 26.8,
28.7 (C6,6'), 29.3 (C3'), 29.5 (C7,7'), 29.8 (C3), 29.9 (C8,8'),
126.0 (C2'), 135.2 (C1'), 137.9 (C1), 142.2 (C2). Found,
%: C 87.73; H 12.27. [M]+ 246. C18H30. Calculated, %:
C 87.62; H 12.25.
Homocyclomagnesation of cycloalkynes with
RMgR' (R, R' = Bu, Et, Br in the presence of
catalyst Cp2ZrCl2. Into a glass reactor under the
atmosphere of dry argon at ~0°C was charg-ed while
stirring 0.5 mmol of Cp2ZrCl2, 10 mmol of cycloalkyne
(cyclooctyne, cyclododecyne), and 20 mmol of RMgR'
(R, R' = Bu, Et, Br) in an appropriate ether solvent. The
temperature was raised to ambient (20–22°C), and the
stirring was continued for 3–8 h. For identification of the
substituted magnesacyclopentadienes by the deuterated
products the reaction mixture was quenched with a 8%
solution of DCl in D2O. The reaction products were
extracted with ether or hexane, the extracts were dried
1-Butyl-2-deutero-1-cyclooctene (VIIIb), bp 109–
111°C (20 mm Hg). H NMR spectrum, δ, ppm: 0.91 t
1
(3H, CH3, J 7 Hz), 1.47 m (12H, CH2), 2.06 m (6H,
CH2CH=C). 13C NMR spectrum, δ, ppm: 14.1 (C12),
22.6 (C11), 26.2 (C6), 26.4 (C5), 26.5 (C4), 28.9 (C7), 29.1
(C3), 30.1 (C10), 30.4 (C9), 37.3 (C8), 123.1 t (C2, J 7 Hz),
141.2 (C1). Found, %: C 86.15; H 12.65; D 1.20. [M]+
167. C12H21D. Calculated, %: C 85.94; H + D 13.50.
1-Ethyl-2-deutero-1-cyclooctene (IXb), bp 75–
1
77°C (20 mm Hg). H NMR spectrum, δ, ppm: 0.90 t
(3H, CH3, J 7 Hz), 1.43 m (8H, CH2), 2.09 m (6H,
CH2CH=C). 13C NMR spectrum, δ, ppm: 13.8 (C10),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009

CYCLOMAGNESATION OF CYCLOALKYNES WITH THE USE OF RMgR'
1603
26.3 (C6), 26.4 (C5), 26.5 (C4), 28.9 (C7), 29.2 (C3), 29.7
(C9), 37.4 (C8), 123.4 t (C2, J 7 Hz), 141.2 (C1). Found,
%: C 86.25; H 12.31; D 1.44. [M]+ 139. C10H17D.
Calculated, %: C 86.01; H + D 13.16.
spectrum, δ, ppm: 0.13 s [9H, (CH3)3Si], 0.92 t (3H, CH3,
J 7 Hz), 1.43 m (12H, CH2), 2.15 m (6H, CH2C=C), 5.47
s (1H, SiCH=C), 5.82 t (1H, CH=C, J 8 Hz). 13C NMR
spectrum, δ, ppm: 0.4 (C15,16,17), 14.1 (C13), 23.1 (C12),
25.9 (C4), 26.1 (C5), 27.1 (C6), 27.6 (C7), 29.1 (C3), 30.3
(C8), 32.6 (C11), 33.5 (C10), 123.4 (C14), 127.0 (C2), 141.7
(C1), 157.9 (C9). Found, %: C 77.19; H 12.19; Si 10.62.
[M]+ 264. C17H32Si. Calculated, %: C 77.04; H 12.15; Si
10.50.
2-Butyl-2'-deutero-1,1'-bi(1-cycloocten-1-yl)
(XIIb), bp 154–156°C (1 mm Hg). 1H NMR spectrum,
δ, ppm: 0.94 t (3H, CH3, J 7 Hz), 1.48 m (20H, CH2),
2.19 m (10H, CH2C=C). 13C NMR spectrum, δ, ppm:
14.1, 22.5, 26.5 (C4,4'), 26.6 (C5,5'), 26.8, 28.8 (C6,6'), 29.3
(C3'), 29.5 (C7,7'), 29.7 (C3), 29.9 (C8,8'), 31.1 (C2'), 135.2
(C1'), 137.9 (C1), 142.2 (C2). Found, %: C 87.20; H 12.07;
D 0.73. [M]+ 275. C20H33D. Calculated, %: C 87.03; H
+ D 12.75.
[1-Deutero-2-(2-deutero1-cycloocten-1-yl)-hex-
1-en-1-yl](trimethyl)silane (XXIId), bp 122–124°C
(1 mm Hg). 1H NMR spectrum, δ, ppm: 0.14 s [9H,
(CH3)3Si], 0.92 t (3H, CH3, J 7 Hz), 1.44 m (12H, CH2),
2.13 m (6H, CH2C=C). 13C NMR spectrum, δ, ppm: 0.4
(C15,16,17), 14.2 (C13), 22.9 (C12), 25.9 (C4), 26.2 (C5),
27.1 (C6), 27.4 (C7), 29.1 (C3), 30.3 (C8), 32.7 (C11), 33.6
(C10), *(C14), *(C2), 141.7 (C1), 157.8 (C9). Found, %:
C 76.61; H 11.35; D 1.51; Si 10.54. [M]+ 266. C17H30D2Si.
Calculated, %: C 76.44; H + D 12.35; Si 10.50.
2-Ethyl-2'-deutero-1,1'-bi(1-cycloocten-1-yl)
(XIIIb), bp 136–138°C (1 mm Hg). 1H NMR spectrum,
δ, ppm: 0.95 t (3H, CH3, J 7 Hz), 1.49 m (16H, CH2),
2.17 m (10H, CH2C=C). 13C NMR spectrum, δ, ppm:
13.9, 26.4 (C4,4'), 26.7 (C5,5'), 26.8, 28.7 (C6,6'), 29.3 (C3'),
29.5 (C7,7'), 29.8 (C3), 29.9 (C8,8'), *(C2'), 135.1 (C1'),
137.9 (C1), 142.2 (C2). Found, %: C 87.37; H 11.81; D
0.81. [M]+ 247. C18H29D. Calculated, %: C 87.12; H +
D 12.45.
Signals marked with asterisk were not observed.
The study was carried out under a financial support
of grants from the President of the Russian Federation
(MK-1039.2007.3 and NSh-2349.2008.3) and of the
Foundation for assistance of domestic science.
3,4-Benzotricyclo[12.6.01,14.06,13]eicosa-
1
1(14),6(13)-diene (XV), mp 158–159°C. H NMR
spectrum, δ, ppm: 1.48–1.68 m (16H, CH2), 2.08–2.48 m
(8H, CH2C=C), 3.02 d (2H, PhCH2C=C, J 13 Hz), 3.76 d
(2H, PhCH2C=C, J 13 Hz), 7.11 m (4H, Ph). 13C NMR
spectrum, δ, ppm: 26.8 (C8,19), 26.9 (C11,16), 28.7 (C9,18),
28.8 (C10,17), 30.4 (C12,15), 30.9 (C7,20), 41.6 (C2,5), 126.3
(C21,24), 129.0 (C13,14), 130.6 (C22,23), 136.7 (C1,6), 139.1
(C3,4). Found, %: C 89.94; H 10.06. [M]+ 320. C24H32.
Calculated, %: C 89.76; H 10.03.
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p. 1388.
Joint cyclomagnesation of cyclic and acyclic
acetylenes with BuMgBr in the presence of catalyst
Cp2ZrCl2. Into a glass reactor under the atmosphere of
dry argon at ~0°C was charged while stirring 1 mmol of
Cp2ZrCl2, 10 mmol of cycloalkyne (cyclooctyne,
cyclododecyne), 11 mmol of disubstituted acetylene, and
22 mmol of BuMgBr in THF. The temperature was raised
to ambient (20–22°C), and the stirring was continued for
3–8 h. For identification of the substituted magnesacyclo-
pentadienes by the deuterated products the reaction
mixture was quenched with a 8% solution of DCl in D2O.
The reaction products were extracted with ether or
hexane, the extracts were dried with MgSO4, and
subjected to fractional distillation.
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