Synthesis and transformations of metallacycles 31. Catalysts based on cobalt complexes in reactions of trialkyl- and alkylhaloalanes with olefins, allenes, and acetylenes

Article abstract of DOI:10.1023/B:RUCB.0000012366.05437.af

Cobalt-containing complexes capable of catalyzing reactions of trialkyl- and alkylhaloalanes (R_nAlCl_3-n) with olefins, allenes, and acetylenes were synthesized. The reactions afford cyclic and acyclic organoaluminum compounds.

Full text of DOI:10.1023/B:RUCB.0000012366.05437.af

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Russian Chemical Bulletin, International Edition, Vol. 52, No. 11, pp. 2434—2439, November, 2003
Synthesis and transformations of metallacycles
31.* Catalysts based on cobalt complexes in reactions of trialkylꢀ and alkylhaloalanes
with olefins, allenes, and acetylenes
A. G. Ibragimov, L. O. Khafizova,ꢀ G. N. Gil´fanova, L. R. Yakupova, A. L. Borisova, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Academy of Sciences of the Bashkortostan Republic
and Ufa Scientific Center of the Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347 2)31 2750. Eꢀmail: ink@anrb.ru
Cobaltꢀcontaining complexes capable of catalyzing reactions of trialkylꢀ and alkylhaloalanes
(RnAlCl3ꢀn) with olefins, allenes, and acetylenes were synthesized. The reactions afford cyclic
and acyclic organoaluminum compounds.
Key words: catalysis; hydroꢀ, cycloꢀ, carboꢀ, and dialumination; organoaluminum comꢀ
pounds; olefins; cobalt complexes; deuterolysis.
Scheme 1
Reactions of hydroꢀ, carboꢀ, and cycloalumination of
unsaturated compounds by trialkylꢀ and alkylhaloalanes
are known2,3 to occur in the presence of Tiꢀ or Zrꢀconꢀ
taining catalysts. The use of metal complexes of other
transition metals as catalysts has not been described.
In this work, with the purpose of searching for new
catalytic systems for these reactions and reactions of
organoaluminum compounds (OAC) with olefins, dienes,
and acetylenes, we studied the reactions of trialkylꢀ and
alkylhaloalanes with unsaturated compounds in the presꢀ
ence of the Fe, Co, Ni, Pd, Rh, Ir, and rareꢀearth metal
(Pr, Ho, Gd) complexes, which are most widely used in
reactions of olefins and dienes.
Results and Discussion
R = Ph (a), oꢀTol (b), pꢀTol (c); R´ = Et, Et2N,
[Co] = CoCl2 + 2 Ph3P, Co(acac)2 + 2 Ph3P
, MeO, BunO
It has been established for the reaction of styrene with
EtAlCl2 that in the presence of metallic magnesium, which
acts as an acceptor of chloride ions, cobalt phosphine
complexes ([Co]) catalyze cycloꢀ and hydroalumination
(CoCl2 : Ph3P = 1 : 2, 10 mol.%, 20—21 °C, 8—10 h,
THF) to form OAC 1а and 2а in a ratio of ∼1 : 3 in an
overall yield of ∼70% (Scheme 1). The structures of the
products of deuterolysis 3а and 4a were proved by specꢀ
troscopic methods and comparison with authentic comꢀ
pounds.4,5
For studying the catalytic activity and structural selecꢀ
tivity of the cobalt phosphine complex, we investigated
the reactions of EtAlCl2 with oꢀ and pꢀmethylstyrene.
Under the chosen conditions, we obtained OAC 1b,c and
2b,c in a ratio of ∼1 : 3 in an overall yield of ∼65%. In
addition to OAC 1 and 2, regioisomeric 2,4ꢀ and 2,5ꢀdiꢀ
arylalumacyclopentanes are formed,6 whose overall yield
does not exceed 15%.
It is assumed that the precursors of 2ꢀarylꢀ1ꢀethylꢀ
alumacyclopropanes 1 in these reactions are cobaltacycloꢀ
propane intermediates, which were previously identified
in the cyclodimerization of acetylenes with nitriles.7 The
intermediate cobalt hydride complexes can be responsible
for the formation of acyclic OAC 2. These intermediates
are formed under the reaction conditions via the mechaꢀ
nism analogous to that proposed previously8 for the synꢀ
thesis of titanium hydride complexes.
When EtAlCl2 is replaced by R´AlCl2 (R´ = Et2N,
1ꢀpiperidyl, MeO, BunO) in the reaction with styrene
* For Part 30, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2302—2306, November, 2003.
1066ꢀ5285/03/5211ꢀ2434 $25.00 © 2003 Plenum Publishing Corporation

Synthesis and reactions of metallacycles
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 11, November, 2003 2435
Scheme 3
(10 mol.% CoCl2+Ph3P, THF, 20—21 °C, 8—10 h),
heterocyclic and acyclic OAC 1a and 2a are formed in a
ratio of ∼1 : 4 in an overall yield of 60—65%.
The reaction of styrene with a twofold excess of
Et2AlCl in the presence of Mg and 10 mol.% of the cobalt
phosphine complex СоСl2+Ph3P (THF, ∼20 °C, 8 h)
afforded 1ꢀphenylꢀ1,2ꢀbis(diethylaluminio)ethane (5) and
1ꢀphenylꢀ2ꢀ(diethylaluminio)ethane (6) in a ratio of ∼2 : 3
in an overall yield of ∼75%. The structures of these comꢀ
pounds were established by the deuterolysis products
(Scheme 2). Regioisomeric diphenylꢀ1,4ꢀdideuterioꢀ
butanes (5—12%) were identified along with 1ꢀphenylꢀ
1,2ꢀdideuterioethane (3а) and 1ꢀphenylꢀ2ꢀdeuterioꢀ
ethane (4а).
Scheme 2
R = Prn (a), nꢀC5H11 (b)
The reactions of alkaꢀ1,2ꢀdienes with EtAlCl2 in THF
at 20 °C for 8 h in the presence of activated magnesium
and cobalt phosphine complexes taken in the molar ratio
RCH=C=CH2 : EtAlCl2 : Mg : [Co] = 10 : 13 : 12 : 1
afford a mixture of unsaturated cyclic OAC 10—12 in
an overall yield of 60—65% (10 : 11 : 12 ≈ 4 : 1 : 15)
(Scheme 4). Monodeuterioolefins were identified
(8—12%) by mass spectrometry of the deuterolysis prodꢀ
ucts of OAC 10—12 along with dideuterioolefins 13—15,
indicating that the competitive hydroalumination of
allenes with the cobalt phosphine complexes occurs, most
likely, along with cycloalumination.
Unlike arylꢀsubstituted αꢀolefins, the reactions of
αꢀalkenes with EtAlCl2 or Et2AlCl in the presence of
10 mol.% СоCl2+Ph3P and metallic magnesium proceed
via hydroalumination to form dialkylethylalanes 7а,b and
alkyldiethylalanes 8а,b (Scheme 3). The structures of comꢀ
pounds 7 and 8 were proved by the identification of their
hydrolysis and deuterolysis products and by oxidation to
the corresponding primary alcohols 9.5
The reaction of Et2AlCl with octꢀ4ꢀyne or styrene in
THF at ∼20 °C in the presence of the CoCl2+Ph3P
catalyst
and
activated
metallic
magnesium
([Al]:RC≡CR : Mg : [Co] = 22 : 10 : 22 : 1) affords unsatꢀ
Scheme 4
R = nꢀC6H13 (a), nꢀC8H17 (b)

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Ibragimov et al.
Scheme 5
R = Prn (a), Ph (b)
urated acyclic OAC 16, 17, and hexasubstituted benzene
(18) in a ratio of ∼3 : 1 : 1 in an overall yield of ∼65%. The
deuterolysis of OAC 16 and 17 produces partially deuterꢀ
ated olefins 19 and 20 (Scheme 5).
yield of ∼50%. This reaction was studied for styrene
(Scheme 7).
Scheme 7
The cobalt phosphine complexes were found to cataꢀ
lyze reactions of unsaturated compounds with EtAlCl2 or
Et2AlCl and also with Et3Al. The reactions of αꢀalkenes
with Et3Al in the presence of catalytic amounts of
Cp2ZrCl2 afford 3ꢀalkylꢀsubstituted alumacyclopentanes.9
In the case of arylꢀsubstituted αꢀolefins10 and norbornene
and its derivatives,11 the reaction proceeds via cycloꢀ
alumination. However, in the presence of the twoꢀcomꢀ
ponent CoCl2+Ph3P catalyst, depending on the structure
of the starting olefin, the reaction proceeds via hydroꢀ
alumination or as hydroꢀ and carboalumination. For exꢀ
ample, αꢀalkenes react with AlEt3 in the presence of
10 mol.% CoCl2+Ph3P to form hydroalumination prodꢀ
ucts 8а,b in a 90—95% yield (Scheme 6).
The compounds of the norbornene series form the
hydroꢀ and carboalumination products in a ratio of ∼3 : 1
in an overall yield of 70—75% (Scheme 8).
Scheme 6
Based on the results obtained, we can conclude that
the cobalt phosphine complexes catalyze the reactions of
trialkylꢀ and alkylhaloalanes with olefins, 1,2ꢀdienes, and
acetylenes to form both cyclic (alumacyclopropanes,
alumacyclopentanes) and acyclic (1,2ꢀdialuminioethyleꢀ
nes, 1,4ꢀdialuminiobutaꢀ1,3ꢀdienes) OAC in high yields.
The cobalt phosphine complexes are analogous, to a great
extent, to the titaniumꢀ and zirconiumꢀcontaining cataꢀ
lysts by the catalytic properties and structural selectivity.
Therefore, they can successfully be used in the hydroꢀ,
carboꢀ, and cycloalumination of olefins and acetylenes.
R = Prn (a), nꢀC5H11 (b)
Under the same conditions, arylꢀsubstituted αꢀolefins
form the products of both hydroalumination of 6 and
carboalumination of 21 in a ratio of ∼1 : 2 in an overall

Synthesis and reactions of metallacycles
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 11, November, 2003 2437
Схема 8
23
R1
R2
24
R1
R2
25
R1
R2
R1
R2
a
b
c
d
H
Et
AlEt2
AlEt2
AlEt2
AlEt2
H
a
b
c
H
Et
H
H
H
Et
a
b
c
d
H
D
Et
D
D
H
D
26a
26b
27a
27b
H
Et
H
AlEt2
AlEt2
H
Et
Et
Et
H
R1 = H (28a), Et (28b)
(10 mmol), and Et2AlCl (22 mmol) were placed in a reactor.
Then the reaction was carried out similarly to variant A.
Experimental
Reactions with organoaluminum compounds were carried
out in a dry argon flow. Solvents were distilled over LiAlH4 prior
to use. Commercial Et3Al (95%), EtAlCl2 (86%), and Et2AlCl
(86%) (Redkinskii Opytnyi Zavod JointꢀStock Company) were
used. The hydrolysis and deuterolysis products were analyzed by
GLC on a Chromꢀ5 chromatograph (He, columns 1200×3 mm,
5% SEꢀ30 or 15% PEGꢀ6000 on Chromaton NꢀAW). IR spectra
were measured on an IRꢀ75 spectrometer (in films). 1Н and
13С NMR spectra were recorded in CDCl3 on JEOL FXꢀ90 Q
spectrometers (89.55 MHz (Н1) and 22.5 MHz (С13), respecꢀ
tively). Starting aluminum amides and alkoxides were syntheꢀ
sized by known procedures.12,13 Compounds 3а—с, 4а—с, 9а,b,
13а,b, 14a,b, 15a,b, 18, 19а,b, and 20а,b were identified by
comparison with authentic samples.1,4—6,14,15 It was difficult to
obtain the 1Н and 13С NMR spectra of the synthesized OAC
because of strong signal broadening due to admixtures of the
intermediate paramagnetic Со2+ complexes (I = 7/2).
Reactions of olefins with EtAlCl2—Mg—[Co] and
Et2AlCl—Mg—[Co]. A. The CoCl2+Ph3P catalyst (1 mmol),
Mg powder (12 mmol), THF (10 mL), olefin (10 mmol), and
EtAlCl2 (12 mmol) were placed in a glass reactor in a dry argon
atmosphere at –5 °C. The solution was heated to ∼20 °C and
stirred for 8 h. The reaction mixture was treated with 10% HCl
or 10% DCl in D2O. The products were extracted with ether or
hexane and isolated by distillation.
Reactions of allenes with EtAlCl2—Mg—[Co]. C. Under the
conditions of method A, the CoCl2+2Ph3P catalyst (1 mmol),
Mg powder (12 mmol), THF (10 mL), allene (10 mmol), and
EtAlCl2 (12 mmol) were placed in a glass reactor. The solution
was heated to ∼20 °C and stirred for 8 h. Then the reaction
mixture was treated as described in method А. The products
were extracted with ether or hexane and isolated by distillation.
Reactions of acetylenes with Et2AlCl—Mg—[Co]. D. Under
the conditions of method A, the CoCl2+Ph3P catalyst (1 mmol),
Mg powder (22 mmol), THF (10 mL), acetylene (10 mmol),
and Et2AlCl (22 mmol) were placed in a glass reactor. The
solution was heated to ∼20 °C and stirred for 8 h. The reaction
mixture was treated as described in method A. The products
were extracted with ether or hexane and isolated by distillation.
Reactions of olefins and norbornenes with Et3Al. E. Under
the conditions of method A, CoCl2+Ph3P (1 mmol), hexane
(10 mL), olefin or the corresponding norbornene (10 mmol),
and Et3Al (12 mmol) were placed in a glass reactor. The solution
was heated to ∼20 °C and stirred for 8 h. The reaction mixture
was treated as described in method A. The products were exꢀ
tracted with ether or hexane and isolated by distillation.
1ꢀDeuteriomethylpropylbenzene (22), b.p. 59—60 °C
(10 Torr) (see Ref. 16). IR, ν/cm–1: 710, 800, 1010, 1050, 1350,
1450, 1500, 1600, 2165 (νСD), 2420, 2860, 2940, 3050. 1Н NMR
(CDCl3), δ: 0.87 (t, 3 Н, Me, J = 7.5 Hz); 1.20 (d, 2 Н, СН2D,
J = 7.0 Hz); 2.60—2.78 (m, Н, СН); 6.80—7.20 (m, 5 Н,
СН arom.). 13С NMR (CDCl3), δ: 12.49 (q, С(3)); 22.54 (t,
B. Under the same conditions, the CoCl2+Ph3P catalyst
(1 mmol), Mg powder (22 mmol), THF (10 mL), olefin

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Ibragimov et al.
С(4), J = 19.5 Hz); 32.56 (t, С(2)); 42.15 (d, С(3)); 125.61
(d, С(4)); 127.54 (d, С(2), C(6)); 128.25 (d, С(3), C(5));
141.10 (d, С(1)).
12.86 (q, С(5″)); 29.64 (t, С(5´)); 32.86 (d, С(3)); 35.54 (d,
С(6), J = 19.5 Hz); 39.58 (d, С(4)); 39.96 (t, С(7)); 40.00
(d, С(1)); 42.85 (d, С(5)); 44.15 (d, С(2)); 63.80 (t, С(2´)).
13С NMR (CDCl3), δ, exoꢀ25c: 12.85 (q, С(5″)); 29.60
(t, С(5´)); 33.95 (t, С(7)); 35.79 (d, С(6), J = 19.5 Hz); 36.10
(t, С(3)); 38.02 (d, С(4)); 40.10 (d, С(2)); 45.61 (d, С(1));
66.32 (t, С(2´)).
endoꢀ2ꢀHydroxymethylꢀexoꢀ6ꢀethylꢀexoꢀ5ꢀdeuteriobiꢀ
cyclo[2.2.1]heptane (endoꢀ25d) and exoꢀ2ꢀhydroxymethylꢀexoꢀ6ꢀ
ethylꢀexoꢀ5ꢀdeuteriobicyclo[2.2.1]heptane (exoꢀ25d). 13С NMR
(CDCl3), δ, endoꢀ25d: 12.68 (q, С(6″)); 27.52 (t, С(6´)); 32.11
(t, С(7)); 34.60 (t, С(3)); 38.57 (d, С(4)); 38.94 (d, С(6)); 40.92
(d, С(5), J = 19.5 Hz); 42.20 (t, С(2)); 44.00 (d, С(1)); 63.18
(t, С(2´)). 13С NMR (CDCl3), δ, exoꢀ25d: 12.70 (q, С(6″));
27.61 (t, С(6´)); 32.03 (t, С(7)); 36.56 (t, С(3)); 38.58 (d, С(4));
39.20 (d, С(6)); 39.81 (d, С(2)); 40.52 (d, С(5), J = 19.5 Hz);
46.15 (d, С(1)); 66.30 (t, С(2´)).
endoꢀ2ꢀHydroxymethylbicyclo[2.2.1]heptane (endoꢀ24a) and
exoꢀ2ꢀhydroxymethylbicyclo[2.2.1]heptane (exoꢀ24a) (∼5 : 1),
b.p. 74—75 °C (5 Torr) (see Ref. 17). IR, ν/cm–1: 710, 1005,
1050, 1450, 2850, 2340, 3310. 1Н NMR (CDCl3), δ: 0.38—2.09
(m, 11 Н, СН, СН2); 3.11—3.44 (m, 2 Н, СН2OH). 13С NMR
(CDCl3), δ, endoꢀ24a: 22.47 (t, С(6)); 29.82 (t, С(5)); 33.60
(d, С(3)); 36.59 (t, С(4)); 37.82 (d, С(1)); 39.71 (t, С(7)); 42.31
(d, С(2)); 64.48 (t, С(2´)). 13С NMR (CDCl3), δ, exoꢀ24a:
28.85 (t, С(5)); 29.82 (t, С (6)); 33.99 (t, С(7)); 35.03 (d, С(4));
36.07 (t, С(3)); 38.02 (d, С(2)); 44.65 (d, С(1)); 66.37 (t, С(2´)).
endoꢀ2ꢀHydroxymethylꢀexoꢀ5ꢀethylbicyclo[2.2.1]heptane
(endoꢀ24b)
and
exoꢀ2ꢀhydroxymethylꢀexoꢀ5ꢀethylbicycꢀ
lo[2.2.1]heptane (exoꢀ24b) (∼5 : 1), b.p. 83—84 °C (1 Torr). IR,
ν/cm–1: 710, 960, 1010, 1050, 1450, 2850, 2930, 3310. 1Н NMR
(CDCl3), δ: 0.86 (t, 3 Н, Me, J = 7.0 Hz); 1.06—1.99 (m, 11 Н,
СН, СН2); 3.10—3.45 (m, 2 Н, СН2ОН). 13С NMR (CDCl3),
δ, endoꢀ24b: 12.89 (q, C(5″)); 29.61 (t, С(5´)); 32.83 (t, С(3));
35.81 (t, С(6)); 39.60 (d, С(4)); 39.77 (t, С(7)); 40.02 (d, С(1));
42.86 (d, С(5)); 44.17 (d, С(2)); 63.81 (t, С(2´)). 13С NMR
(CDCl3), δ, exoꢀ24b: 12.89 (q, (5″)); 29.61 (t, С(5´)); 33.96
(t, С(7)); 36.11 (t, С(3)); 36.15 (d, С(6)); 38.04 (d, С(4)); 40.10
(d, С(2)); 40.92 (d, С(5)); 45.63 (d, С(1)); 66.35 (t, С(2´)).
endoꢀ2ꢀHydroxymethylꢀexoꢀ6ꢀethylbicyclo[2.2.1]heptane
Pentacyclo[8.2.1.14,7.02,9.03.8]tetradecꢀ11ꢀene (27a). IR,
ν/cm–1: 720, 750, 920, 2870, 2940, 3060. 1Н NMR (CDCl3), δ:
0.94—1.98 (m, 14 Н, СН2, СН); 2.54—2.57 (m, 2 Н, СН);
5.88—5.97 (m, 2 Н, СН=СН). 13С NMR (CDCl3), δ: 27.82 (t,
С(5), C(6)); 33.73 (t, С(14)); 38.92 (t, С(13)); 41.52 (d, С(3),
C(8)); 43.16 (d, С(2), C(9)); 44.26 (d, С(7), C(11)); 45.43 (d,
С(1), C(10)); 135.28 (d, С(11), C(12)).
exoꢀ5ꢀEthylpentacyclo[8.2.1.14,7.02,9.03.8]tetradecꢀ11ꢀene
(27b). IR, ν/cm–1: 710, 1345, 1475, 2930, 2950, 3070. 1Н NMR
(CDCl3), δ: 0.86 (t, 3 Н, Me, J = 7.0 Hz); 1.06—1.97 (m, 15 Н,
СН, СН2); 5.53—5.96 (m, 2 Н, СН=СН). 13С NMR (CDCl3),
δ: 12.53 (q, С(5″)); 29.30 (t, С(5´)); 30.73 (t, С(14)); 36.26
(t, С(6)); 39.51 (d, С(2), C(9)); 39.90 (t, С(13)); 40.49 (d, С(8));
41.53 (d, С(3)); 42.31 (d, С(5)); 43.55 (d, С(1), C(10)); 43.81
(d, С(4)); 44.26 (d, С(11), C(12)).
(endoꢀ24c)
and
exoꢀ2ꢀhydroxymethylꢀexoꢀ6ꢀethylbicycꢀ
lo[2.2.1]heptane (exoꢀ24c) (~5 : 1). 13С NMR (CDCl3), δ,
endoꢀ24c: 12.68 (q, C(6″)); 27.52 (t, С(6´)); 32.14 (t, С(7));
34.62 (t, С(3)); 38.57 (d, С(4)); 38.96 (t, С(6)); 41.24 (d, С(5));
42.18 (d, С(2)); 44.02 (d, С(1)); 63.20 (t, С(2´)). 13С NMR
(CDCl3), δ, exoꢀ24c: 12.68 (q, C(6″)); 27.52 (t, С(6´)); 31.90
(t, С(7)); 36.54 (t, С(3)); 38.57 (d, С(4)); 39.05 (t, С(2)); 39.18
(d, С(6)); 40.84 (t, С(5)); 46.12 (d, С(1)); 66.35 (t, С(2´)).
endoꢀ2ꢀHydroxymethylꢀexoꢀ6ꢀdeuteriobicyclo[2.2.1]heptane
(endoꢀ25a) and exoꢀ2ꢀhydroxymethylꢀexoꢀ6ꢀdeuteriobicycꢀ
lo[2.2.1]heptane (exoꢀ25a) (∼5 : 1), b.p. 74—75 °C (5 Torr) (see
Ref. 17). IR, ν/cm–1: 710, 1005, 1050, 1450, 2170 (νСD), 2850,
2930, 3310. 1Н NMR (CDCl3), δ: 0.32—2.03 (m, 10 Н, СН,
CHD, СН2); 3.11—3.44 (m, 2 Н, СН2OH). 13С NMR (CDCl3),
δ, endoꢀ25a: 22.17 (d, С(6), J = 19.5 Hz); 29.78 (t, С(5)); 33.56
(d, С(3)); 36.57 (t, С(4)); 37.79 (d, С(1)); 39.68 (t, С(7)); 42.30
(d, С(2)); 64.48 (t, С(2´)). 13С NMR (CDCl3), δ, exoꢀ25a:
28.83 (t, С(5)); 29.57 (t, С(6), J = 19.5 Hz); 33.86 (t, С(7));
34.93 (d, С(4)); 36.00 (t, С(3)); 37.96 (d, С(2)); 44.39 (d, С(1));
66.34 (t, С(2´)).
exoꢀ6ꢀDeuteriopentacyclo[8.2.1.14,7.02,9.03.8]tetradecꢀ11ꢀ
ene (28a).. IR, ν/cm–1: 720, 750, 920, 2165 (νСD), 2870, 2940,
3060. 1Н NMR (CDCl3), δ: 0.94—1.98 (m, 13 Н, СН2, СН2D,
CH); 2.54—2.57 (m, 2 Н, СН); 5.88—5.97 (m, 2 Н, СН=СН).
13С NMR (CDCl3), δ: 27.61 (d, С(6), J = 19.5 Hz); 27.81
(t, С(5)); 33.73 (t, С(14)); 38.93 (t, С(13)); 41.53 (d, С(3),
C(8)); 43.16 (d, С(2), C(9)); 44.26 (d, С(7), C(11)); 45.43 (d,
С(1), C(10)); 135.30 (d, С(11), C(12)).
exoꢀ5ꢀEthylꢀexoꢀ6ꢀdeuteriopentacyclo[8.2.1.14,7
2,9.03.8]tetradecꢀ11ꢀene (28b). IR, ν/cm–1: 705, 1345, 1470,
.
0
2165 (νСD), 2930, 2950, 3070. 1Н NMR (CDCl3), δ: 0.86 (t,
3 Н, Me); 1.06—1.97 (m, 14 Н, СН, СН2, СНD); 5.53—5.96
(m, 2 Н, СН=СН). 13С NMR (CDCl3), δ: 12.59 (q, С(5″));
29.30 (t, С(5´)); 30.73 (t, С(14)); 35.94 (d, С(6), JС,D = 19.5 Hz);
39.38 (t, С(13)); 39.97 (d, С(3)); 40.49 (d, С(2), C(9)); 41.59
(d, С(8)); 42.70 (d, С(5)); 43.55 (d, С(1), C(10)); 43.81
(d, С(4)); 44.26 (d, С(6)); 135.37 (d, С(11), C(12)).
endoꢀ2ꢀHydroxymethylꢀexoꢀ5ꢀdeuteriobicyclo[2.2.1]heptane
(endoꢀ25b) and exoꢀ2ꢀhydroxymethylꢀexoꢀ5ꢀdeuteriobicycꢀ
lo[2.2.1]heptane (exoꢀ25b) (∼5 : 1). 13С NMR (CDCl3), δ,
endoꢀ25b: 22.47 (t, С(6)); 29.36 (t, С(5)); 33.56 (d, С(3)); 36.57
(t, С(4)); 37.79 (d, С(1)); 39.68 (t, С(7)); 42.30 (d, С(2)); 64.48
(t, С(2´)). 13С NMR (CDCl3), δ, exoꢀ25b: 28.51 (d, С(5),
J = 19.5 Hz); 29.80 (t, С(6)); 33.86 (t, С(7)); 34.93 (d, С(4));
36.00 (t, С(3)); 37.96 (d, С(2)); 44.39 (d, С(1)); 66.34 (t, С(2´)).
endoꢀ2ꢀHydroxymethylꢀexoꢀ5ꢀethylꢀexoꢀ6ꢀdeuteriobicycꢀ
lo[2.2.1]heptane (endoꢀ25c) and exoꢀ2ꢀhydroxymethylꢀexoꢀ
5ꢀethylꢀexoꢀ6ꢀdeuteriobicyclo[2.2.1]heptane (exoꢀ25c), b.p.
83—84 °C (1 Torr). IR, ν/cm–1: 710, 960, 1010, 1050, 1450,
2165 (νСD), 2850, 2930, 3315. 1Н NMR (CDCl3), δ: 0.86 (t,
3 Н, Me, J = 7.0 Hz); 1.05—1.98 (m, 10 Н, СН, CHD, СН2);
3.10—3.45 (m, 2 Н, СН2ОН). 13С NMR (CDCl3), δ, endoꢀ25c:
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos. 03ꢀ03ꢀ33050
and 02ꢀ03ꢀ97904).
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Received April 4, 2003;
in revised form June 2, 2003